CN114842996A - Supercritical water oxidation reactor and method suitable for radioactive waste treatment - Google Patents

Supercritical water oxidation reactor and method suitable for radioactive waste treatment Download PDF

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Publication number
CN114842996A
CN114842996A CN202210468294.5A CN202210468294A CN114842996A CN 114842996 A CN114842996 A CN 114842996A CN 202210468294 A CN202210468294 A CN 202210468294A CN 114842996 A CN114842996 A CN 114842996A
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China
Prior art keywords
supercritical water
wall
inlet
reaction
radioactive waste
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CN202210468294.5A
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Inventor
王树众
徐甜甜
孙圣瀚
刘璐
李建娜
杨健乔
李艳辉
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Xian Jiaotong University
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Xian Jiaotong University
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Priority to CN202210468294.5A priority Critical patent/CN114842996A/en
Publication of CN114842996A publication Critical patent/CN114842996A/en
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    • GPHYSICS
    • G21NUCLEAR PHYSICS; NUCLEAR ENGINEERING
    • G21FPROTECTION AGAINST X-RADIATION, GAMMA RADIATION, CORPUSCULAR RADIATION OR PARTICLE BOMBARDMENT; TREATING RADIOACTIVELY CONTAMINATED MATERIAL; DECONTAMINATION ARRANGEMENTS THEREFOR
    • G21F9/00Treating radioactively contaminated material; Decontamination arrangements therefor
    • G21F9/008Apparatus specially adapted for mixing or disposing radioactively contamined material
    • GPHYSICS
    • G21NUCLEAR PHYSICS; NUCLEAR ENGINEERING
    • G21FPROTECTION AGAINST X-RADIATION, GAMMA RADIATION, CORPUSCULAR RADIATION OR PARTICLE BOMBARDMENT; TREATING RADIOACTIVELY CONTAMINATED MATERIAL; DECONTAMINATION ARRANGEMENTS THEREFOR
    • G21F9/00Treating radioactively contaminated material; Decontamination arrangements therefor
    • G21F9/04Treating liquids
    • G21F9/06Processing
    • GPHYSICS
    • G21NUCLEAR PHYSICS; NUCLEAR ENGINEERING
    • G21FPROTECTION AGAINST X-RADIATION, GAMMA RADIATION, CORPUSCULAR RADIATION OR PARTICLE BOMBARDMENT; TREATING RADIOACTIVELY CONTAMINATED MATERIAL; DECONTAMINATION ARRANGEMENTS THEREFOR
    • G21F9/00Treating radioactively contaminated material; Decontamination arrangements therefor
    • G21F9/28Treating solids
    • G21F9/30Processing
    • YGENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02PCLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P20/00Technologies relating to chemical industry
    • Y02P20/50Improvements relating to the production of bulk chemicals
    • Y02P20/54Improvements relating to the production of bulk chemicals using solvents, e.g. supercritical solvents or ionic liquids

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  • Physics & Mathematics (AREA)
  • Engineering & Computer Science (AREA)
  • General Engineering & Computer Science (AREA)
  • High Energy & Nuclear Physics (AREA)
  • Processing Of Solid Wastes (AREA)

Abstract

The invention discloses a supercritical water oxidation reactor and a supercritical water oxidation method suitable for radioactive waste treatment. The bottom is a nuclide salt storage area, and is provided with a mechanical stirring device and a tertiary oxidant inlet. The invention can realize supercritical water oxidation treatment of radioactive wastes, removes nuclide by utilizing the characteristic of low solubility of the nuclide in supercritical water and simultaneously mechanically removes the nuclide by a scraping brush, and simultaneously can absorb the heat of a reaction area to prevent the wall surface from being over-heated and can also utilize the residual heat due to the existence of the cooling film type wall. Meanwhile, a sacrificial thin liner is arranged at a key part of the reactor to ensure that the generation of radioactive wastes after the device is decommissioned is minimized. The reactor has important application value in the field of supercritical water oxidation treatment of radioactive wastes.

Description

Supercritical water oxidation reactor and method suitable for radioactive waste treatment
Technical Field
The invention belongs to the field of radioactive waste treatment, and particularly relates to a supercritical water oxidation reactor and a supercritical water oxidation method suitable for radioactive waste treatment.
Background
As a clean energy, nuclear power becomes an important component in the energy structure of China. With the emergence of a large number of nuclear power stations, the amount of radioactive waste also rises year by year, and mainly comprises radioactive waste ion exchange resin, radioactive waste oil, radioactive waste solvent, radioactive waste protective clothing, gloves and the like. At present, the main methods for treating these radioactive wastes include an incineration method, a plasma incineration method, a fenton oxidation method, a direct solidification method, and the like. However, these methods have various problems, and although the incineration method can significantly reduce the volume of waste, it causes secondary pollution such as radioactive fly ash; the plasma incineration method needs to add a curing material, and a tail gas treatment system is complicated; although the fenton oxidation method has mild reaction conditions, the reaction time is long and the amount of secondary waste liquid is large; the direct curing method has simple process, but has larger compatibilization.
The supercritical water oxidation technology is that under the condition of temperature and pressure exceeding the critical point of water, the special property of supercritical water is utilized to make radioactive organic matter and oxidant produce homogeneous phase oxidation reaction in the supercritical water so as to decompose the radioactive organic matter into CO 2 、H 2 O、N 2 And the radionuclide is converted into inorganic nuclide salt, and the nuclide salt is easily separated by utilizing the characteristic that the solubility of the nuclide salt in supercritical water is extremely low.
Disclosure of Invention
The invention aims to solve the problems in the prior art and provides a supercritical water oxidation reactor and a supercritical water oxidation method suitable for radioactive waste treatment. The reactor has the functions of low-temperature material incidence, alcohol co-oxidation, catalytic oxidation, cold wall protection, waste heat recovery and the like, ensures the solidification and separation of nuclides while efficiently removing radioactive organic matters, and provides a feasible scheme for the treatment of radioactive wastes.
In order to achieve the purpose, the invention adopts the following technical scheme to realize the purpose:
a supercritical water oxidation reactor suitable for radioactive waste treatment comprising:
the end cover part comprises an end part cartridge and an annular cover plate, the end part cartridge is connected to the inner ring of the annular cover plate, and the bottom of the annular cover plate is hermetically connected with the flow-guiding heat-insulating cylinder; the inner cavity of the end part medicine adding cylinder is an end cover area;
the central cylinder is internally provided with a flow guide heat insulation cylinder, the inner cavity of the flow guide heat insulation cylinder is a reaction area, and the reaction area is communicated with the end cover area;
the cooling wall is of a cylindrical structure with an opening at the top and is sleeved at the bottom of the flow guide heat insulation cylinder, an inner cavity formed by the bottom of the flow guide heat insulation cylinder and the inner side of the cooling wall is a salt storage area, and the salt storage area is communicated with the reaction area.
The invention further improves the following steps:
the top of the end cartridge is provided with a high-temperature supercritical water injection port, the side wall of the end cartridge is provided with a primary oxidant inlet and a primary low-temperature material inlet, and the primary oxidant inlet is positioned above the primary low-temperature material inlet; the high-temperature supercritical water injection port, the primary oxidant inlet and the primary low-temperature material inlet are communicated with the end cover area.
An end cover cooling water inlet and an end cover cooling water outlet are formed in the side face of the annular cover plate; the end surface of the annular cover plate is provided with a secondary low-temperature material inlet and a secondary oxidant inlet; the secondary low-temperature material inlet and the secondary oxidant inlet are communicated with the reaction area.
The reaction zone is internally provided with a stirrer and a scraping brush from top to bottom in sequence.
The inner wall of the flow-guiding heat-insulating cylinder is provided with a sacrificial thin liner, the wall of the flow-guiding heat-insulating cylinder is provided with a through hole which is communicated with the inner side of the wall of the central cylinder, and a filtering wall is arranged in the through hole.
A material preheater and a water taking heater are arranged in the wall of the central cylinder; the material preheater and the water taking heater are arranged on the outer side of the flow guide heat insulation cylinder; and a reaction water outlet is formed in the side surface of the central cylinder and communicated with the reaction zone.
A cold wall water inlet, a cold wall water outlet, a tertiary oxidant inlet and a salt discharge port are formed in the side surface of the cooling wall; the tertiary oxidant inlet and the salt discharge port are communicated with the salt storage area; the tertiary oxidant inlet is arranged on the side wall of the cooling wall, and the salt discharge port is arranged at the bottom of the cooling wall.
The filtering wall adopts a filtering net or a sintered metal filter.
The wall of the central cylinder is a membrane wall, a coil pipe or a cooling cavity with a flow guiding function.
A supercritical water oxidation process suitable for radioactive waste treatment comprising the steps of:
injecting supercritical water, a primary oxidant and a primary low-temperature material into the end cover area, and inputting a secondary oxidant and a secondary low-temperature material into the reaction area, so that the primary oxidant, the primary low-temperature material, the secondary oxidant and the secondary low-temperature material are mixed in the reaction area and subjected to oxidation reaction;
after the reaction, the supercritical water passes through the filtering wall, is cooled and depressurized to form steam, and the steam is discharged through the reaction water outlet, and the nuclide is deposited in the salt storage area and discharged through the salt discharge port.
Compared with the prior art, the invention has the following beneficial effects:
1. effectively separating nuclides. Because the solubility of the nuclide in the supercritical water is extremely low, the nuclide is separated from the supercritical water by mechanical means such as scraping and brushing, porous powder sintering walls and the like, so that the nuclide in the radioactive waste can be effectively removed, and the nuclide is prevented from being diffused to the environment. Meanwhile, the process of removing nuclide in the salt storage area can be intermittent and continuous, so that the reactor is suitable for different systems.
2. The center of the reaction zone is high-temperature and is efficiently oxidized. The primary oxidant and the low-temperature material release a large amount of heat after being subjected to confluence reaction at an outlet, and the secondary oxidant and the secondary material are subjected to violent oxidation reaction at the outlet. The temperature is higher, which is beneficial to the full degradation of the radioactive waste.
3. Waste heat utilization and cold wall protection. The existence of the cold wall water can not only absorb the heat generated by the reaction, but also prevent the wall surface from being damaged due to overtemperature, and the heated water can be used for other purposes.
Drawings
In order to more clearly explain the technical solutions of the embodiments of the present invention, the drawings needed to be used in the embodiments will be briefly described below, it should be understood that the following drawings only illustrate some embodiments of the present invention, and therefore should not be considered as limiting the scope, and for those skilled in the art, other related drawings can be obtained according to the drawings without inventive efforts.
FIG. 1 is a schematic view of the structure of the present invention.
Wherein: 1-an end cap region; 2-a stirrer; 3-a flow guiding heat insulation cylinder; 4, scraping and brushing; 5-taking a water heater; 6-a material preheater; 7-a reaction zone; 8-a filtration wall; 9-a sacrificial thin liner; 10-a salt storage area; 11-a stave; n1-high temperature supercritical water injection port; n2-primary oxidant inlet; N3-Primary cryogenic feed Inlet; n4-end cap cooling water inlet; n5-secondary low-temperature material inlet; n6-secondary oxidant inlet; n7-end cover cooling water outlet; n8-cold wall water inlet; n9-reaction water outlet; N10-Cold wall Water Outlet; n11-tertiary oxidant inlet; n12-salt discharge port.
Detailed Description
In order to make the objects, technical solutions and advantages of the embodiments of the present invention clearer, the technical solutions in the embodiments of the present invention will be clearly and completely described below with reference to the drawings in the embodiments of the present invention, and it is obvious that the described embodiments are some, but not all, embodiments of the present invention. The components of embodiments of the present invention generally described and illustrated in the figures herein may be arranged and designed in a wide variety of different configurations.
Thus, the following detailed description of the embodiments of the present invention, presented in the figures, is not intended to limit the scope of the invention, as claimed, but is merely representative of selected embodiments of the invention. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
It should be noted that: like reference numbers and letters refer to like items in the following figures, and thus, once an item is defined in one figure, it need not be further defined and explained in subsequent figures.
In the description of the embodiments of the present invention, it should be noted that if the terms "upper", "lower", "horizontal", "inner", etc. are used for indicating the orientation or positional relationship based on the orientation or positional relationship shown in the drawings or the orientation or positional relationship which is usually arranged when the product of the present invention is used, the description is merely for convenience and simplicity, and the indication or suggestion that the referred device or element must have a specific orientation, be constructed and operated in a specific orientation, and thus, cannot be understood as limiting the present invention. Furthermore, the terms "first," "second," and the like are used merely to distinguish one description from another, and are not to be construed as indicating or implying relative importance.
Furthermore, the term "horizontal", if present, does not mean that the component is required to be absolutely horizontal, but may be slightly inclined. For example, "horizontal" merely means that the direction is more horizontal than "vertical" and does not mean that the structure must be perfectly horizontal, but may be slightly inclined.
In the description of the embodiments of the present invention, it should be further noted that unless otherwise explicitly stated or limited, the terms "disposed," "mounted," "connected," and "connected" should be interpreted broadly, and may be, for example, fixedly connected, detachably connected, or integrally connected; can be mechanically or electrically connected; they may be connected directly or indirectly through intervening media, or they may be interconnected between two elements. The specific meanings of the above terms in the present invention can be understood by those skilled in the art according to specific situations.
The invention is described in further detail below with reference to the accompanying drawings:
referring to fig. 1, the embodiment of the invention discloses a supercritical water oxidation reactor suitable for radioactive waste treatment, which mainly comprises an upper end cover region 1, a middle reaction and waste heat utilization region 7 and a lower nuclide salt storage region 10. The end cover region 1 is provided with a high-temperature supercritical water injection port N1, a primary oxidant injection port N2, a primary low-temperature material inlet N3, an end cover cooling water inlet N4, an end cover cooling water outlet N7, a secondary low-temperature material inlet N5 and a secondary oxidant inlet N6. A cold wall water inlet N8, a cold wall water outlet N10 and a reaction water outlet N9 are arranged outside the reaction zone 7; a diversion heat insulation cylinder 3 with a sacrificial thin liner 9, a material preheater 6 and a water taking heater 5 are sequentially arranged at the inner side of the reaction zone 7, wherein a filtering wall 8 is arranged on the wall of the diversion heat insulation cylinder 3; the core area of the reaction area 7 is provided with mechanical devices such as a scraping brush 4, a stirrer 2 and the like. The bottom is a nuclide salt storage area 10 which is provided with a mechanical stirring device, a tertiary oxidant inlet N11 and a salt discharge port N12.
The radioactive materials are preheated by a material preheater circuit 6 in the reactor, then enter a core reaction area 7 in the reactor through a first upper end cover and a second inlet of the reactor, and are mixed by high-temperature supercritical water to reach reaction conditions, and then supercritical water oxidation reaction is carried out. The oxidant includes, but is not limited to, entering the reactor in three times, and entering the reactor in multiple times according to the reaction condition. A sacrificial thin liner 9 is attached to the inner part of the flow guiding and heat insulating cylinder 3 in the core area of the reactor, and the thin liner 9 can have reaction catalysis function according to different materials. The mechanical device in the reactor core area includes, but is not limited to, a scraper brush 4, a stirrer 2, etc. for mixing the reaction fluid and separating the solid nuclide salt. The filtering wall 8 of the diversion heat insulation cylinder is a filtering wall with tiny pores for separating nuclide salt from supercritical water, and is not limited to a filter screen, a sintered metal filter and the like. The reactor is characterized in that end cover cold wall water is arranged in the upper end cover of the reactor, cylinder wall cold wall water is arranged on the central cylinder wall, and the loading form of the cold wall water is not limited to a membrane wall, a coil pipe, a cooling cavity with a flow guide effect and the like. The material preheater 6 can be arranged in the reactor according to the use requirement, and can also be arranged outside the reactor. The size of the nuclide salt storage area 10 at the lower part of the reactor can be set according to different functions of material nuclide salt content, intermittent salt discharge, continuous salt discharge and the like. The parts of the diversion heat insulation cylinder 3, the material preheater 6, the water taking heater 5 and the like in the reactor are all arranged to be detachable
The working process of the invention is as follows:
supercritical water, primary oxidant and low-temperature material are respectively injected from corresponding injection ports, mixed and generate violent oxidation reaction in the reaction zone 7, and simultaneously, the secondary oxidant and the secondary material are also reacted at the reaction zone. After the reaction, nuclides are separated due to low solubility in supercritical water, the supercritical water passes through the filtering wall 8 and then is cooled and depressurized to form steam, the steam is discharged through a reaction water outlet N9, and the nuclides are deposited in the salt storage area 10 and discharged through a salt discharge port N12.
In summary, aiming at the problems of low degradation efficiency, large nuclide solidification volume and the like based on the traditional radioactive waste treatment method, the invention provides the supercritical water oxidation reactor suitable for radioactive waste treatment, which can realize high-efficiency degradation of the radioactive waste and simultaneously remove the nuclide.
The above is only a preferred embodiment of the present invention, and is not intended to limit the present invention, and various modifications and changes will occur to those skilled in the art. Any modification, equivalent replacement, or improvement made within the spirit and principle of the present invention should be included in the protection scope of the present invention.

Claims (10)

1. A supercritical water oxidation reactor suitable for radioactive waste treatment, comprising:
the end cover part comprises an end part cartridge and an annular cover plate, the end part cartridge is connected to the inner ring of the annular cover plate, and the bottom of the annular cover plate is hermetically connected with the flow guide heat insulation cylinder (3); the inner cavity of the end part medicine adding barrel is an end cover area (1);
the flow-guiding heat-insulating cylinder (3) is arranged in the central cylinder, the inner cavity of the flow-guiding heat-insulating cylinder (3) is a reaction zone (7), and the reaction zone (7) is communicated with the end cover zone (1);
the cooling wall (11), the open-top tubular structure of cooling wall (11) overlaps the bottom at water conservancy diversion heat-insulating cylinder (3), and the inner chamber that the bottom of water conservancy diversion heat-insulating cylinder (3) and cooling wall (11) inboard enclose is for depositing salt district (10), it is linked together with reaction zone (7) to deposit salt district (10).
2. The supercritical water oxidation reactor suitable for radioactive waste treatment according to claim 1, characterized in that the top of the end loading cartridge is opened with a high temperature supercritical water injection port (N1), the side wall is opened with a primary oxidant inlet (N2) and a primary low temperature material inlet (N3), the primary oxidant inlet (N2) is located above the primary low temperature material inlet (N3); the high-temperature supercritical water injection port (N1), the primary oxidant inlet (N2) and the primary low-temperature material inlet (N3) are communicated with the end cover area (1).
3. Supercritical water oxidation reactor suitable for radioactive waste treatment according to claim 1 or 2, characterized by the fact that the side of the annular cover plate is provided with an end cap cooling water inlet (N4) and an end cap cooling water outlet (N7); the end surface of the annular cover plate is provided with a secondary low-temperature material inlet (N5) and a secondary oxidant inlet (N6); the secondary low-temperature material inlet (N5) and the secondary oxidant inlet (N6) are communicated with the reaction zone (7).
4. Supercritical water oxidation reactor suitable for radioactive waste treatment according to claim 1, characterized by the fact that inside the reaction zone (7) there are placed in sequence from top to bottom a stirrer (2) and a scraping brush (4).
5. The supercritical water oxidation reactor for radioactive waste treatment according to claim 1, characterized in that the inner wall of the flow guiding and heat insulating cylinder (3) is provided with a sacrificial thin liner (9), the wall of the flow guiding and heat insulating cylinder (3) is provided with through holes communicated with the inner side of the wall of the central cylinder, and the through holes are provided with filter walls (8).
6. Supercritical water oxidation reactor suitable for the treatment of radioactive wastes according to claim 1, 4 or 5, characterized in that inside the wall of the central cylinder there are provided a material preheater (6) and a water-taking heater (5); the material preheater (6) and the water taking heater (5) are arranged on the outer side of the flow guide heat insulation cylinder (3); a reaction water outlet (N9) is arranged on the side surface of the central cylinder, and the reaction water outlet (N9) is communicated with the reaction zone (7).
7. The supercritical water oxidation reactor suitable for radioactive waste treatment according to claim 1, characterized in that the cooling wall (11) is provided with a cold wall water inlet (N8), a cold wall water outlet (N10), a tertiary oxidant inlet (N11) and a salt discharge outlet (N12) at its side; the tertiary oxidant inlet (N11) and the salt discharging port (N12) are communicated with the salt storage area (10); the tertiary oxidant inlet (N11) is arranged on the side wall of the cooling wall (11), and the salt discharge port (N12) is arranged at the bottom of the cooling wall (11).
8. Supercritical water oxidation reactor suitable for the treatment of radioactive wastes according to claim 1, characterized in that the filtering wall (8) is a filtering net or a sintered metal filter.
9. The supercritical water oxidation reactor suitable for radioactive waste treatment according to claim 1, characterized in that the wall of the central drum is a membrane wall, a coil or a cooling chamber with flow guiding function.
10. A supercritical water oxidation process suitable for radioactive waste treatment using a reactor according to any one of claims 1 to 9, characterized by the following steps:
injecting supercritical water, a primary oxidant and a primary low-temperature material into the end cover area (1), and inputting a secondary oxidant and a secondary low-temperature material into the reaction area (7), so that the primary oxidant, the primary low-temperature material, the secondary oxidant and the secondary low-temperature material are mixed in the reaction area (7) and generate an oxidation reaction;
after the reaction, the supercritical water passes through the filtering wall (8), is cooled and depressurized to form steam, and the steam is discharged through a reaction water outlet (N9), and nuclides are deposited in the salt storage area (10) and discharged through a salt discharge port (N12).
CN202210468294.5A 2022-04-29 2022-04-29 Supercritical water oxidation reactor and method suitable for radioactive waste treatment Pending CN114842996A (en)

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CN202210468294.5A CN114842996A (en) 2022-04-29 2022-04-29 Supercritical water oxidation reactor and method suitable for radioactive waste treatment

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Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN108837792A (en) * 2018-08-14 2018-11-20 成都九翼环保科技有限公司 A kind of complete waterpower mixed type overcritical water oxidization reactor and its application in sewage recycling utilization

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN108837792A (en) * 2018-08-14 2018-11-20 成都九翼环保科技有限公司 A kind of complete waterpower mixed type overcritical water oxidization reactor and its application in sewage recycling utilization
CN108837792B (en) * 2018-08-14 2023-07-21 成都九翼环保科技有限公司 Complete hydraulic hybrid supercritical water oxidation reactor and application thereof in sewage resource utilization

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