CN113643837A - Mineralization-oxidation treatment process for radioactive TBP/OK organic waste liquid - Google Patents
Mineralization-oxidation treatment process for radioactive TBP/OK organic waste liquid Download PDFInfo
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- G—PHYSICS
- G21—NUCLEAR PHYSICS; NUCLEAR ENGINEERING
- G21F—PROTECTION AGAINST X-RADIATION, GAMMA RADIATION, CORPUSCULAR RADIATION OR PARTICLE BOMBARDMENT; TREATING RADIOACTIVELY CONTAMINATED MATERIAL; DECONTAMINATION ARRANGEMENTS THEREFOR
- G21F9/00—Treating radioactively contaminated material; Decontamination arrangements therefor
- G21F9/04—Treating liquids
- G21F9/06—Processing
-
- G—PHYSICS
- G21—NUCLEAR PHYSICS; NUCLEAR ENGINEERING
- G21F—PROTECTION AGAINST X-RADIATION, GAMMA RADIATION, CORPUSCULAR RADIATION OR PARTICLE BOMBARDMENT; TREATING RADIOACTIVELY CONTAMINATED MATERIAL; DECONTAMINATION ARRANGEMENTS THEREFOR
- G21F9/00—Treating radioactively contaminated material; Decontamination arrangements therefor
- G21F9/04—Treating liquids
- G21F9/06—Processing
- G21F9/16—Processing by fixation in stable solid media
- G21F9/162—Processing by fixation in stable solid media in an inorganic matrix, e.g. clays, zeolites
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- Engineering & Computer Science (AREA)
- General Engineering & Computer Science (AREA)
- High Energy & Nuclear Physics (AREA)
- Chemical & Material Sciences (AREA)
- Inorganic Chemistry (AREA)
- Processing Of Solid Wastes (AREA)
Abstract
The invention relates to the field of radioactive organic waste liquid treatment, which is used for efficiently solving the difficult problems of mineralization and fixation of phosphorus and inorganic treatment of organic components in TBP/OK organic waste liquid, in particular to a process for mineralizing and fixing phosphorus and inorganic oxidation of radioactive TBP/OK organic waste liquid, wherein the reaction process is divided into two stages, firstly, the organic waste liquid is added into a primary mineralization reactor, TBP is cracked into small molecular products, and phosphorus-containing components are mineralized and fixed to generate products with more stable properties; OK and the micromolecule product are gasified and enter a secondary oxidation reactor together, and oxidation reaction is carried out to generate carbon dioxide and water. The process realizes mineralization and fixation of phosphorus elements while efficiently cracking TBP, thoroughly oxidizes organic components into inorganic substances at low temperature, reduces or eliminates the negative influence of the phosphorus elements in the conventional pyrolysis incineration process, can construct a process flow and complete equipment which are simple and convenient to operate, safe and controllable, and realizes safe and efficient mineralization and phosphorus fixation of TBP/OK organic waste liquid and inorganic oxidation treatment.
Description
Technical Field
The invention relates to the technical field of radioactive organic waste liquid treatment, is used for efficiently solving the difficult problems of mineralization fixation of phosphorus and inorganic treatment of organic components in TBP/OK organic waste liquid, and particularly relates to a process for mineralization fixation of phosphorus and inorganic oxidation of radioactive TBP/OK organic waste liquid.
Background
TBP/OK is widely used as an extracting agent of U, Pu in the recycling production process of nuclear fuel, and the composition (volume ratio) of the TBP/OK is as follows: 30% of tributyl phosphate (TBP) and 70% of hydrogenated kerosene (OK). TBP is an extractant with excellent performance and the molecular formula of (C)4H9O)3PO; the hydrogenated kerosene is saturated hydrocarbon kerosene subjected to catalytic hydrogenation treatment.
The radioactive TBP/OK organic waste liquid mainly comes from uranium purification sections and post-treatment uranium and plutonium separation sections of nuclear fuel production plants and military nuclear facilities, contains various fission nuclides and plutonium and uranium with certain concentration, and must be properly treated as waste. Because an efficient and safe treatment technology is not mastered in China, the radioactive TBP/OK organic waste liquid is basically in a temporary storage state. The amount of radioactive organic waste liquid accumulated during several decades of operation in nuclear fuel plants and military nuclear facilities has been quite large. In addition, more radioactive organic waste liquid is generated after the newly-built nuclear fuel post-treatment project is put into operation, and the temporary storage pressure and the potential safety hazard are increasingly highlighted. Research on harmless treatment of radioactive organic waste liquid is an important problem to be solved urgently in the nuclear fuel production process.
In the uranium purification and spent fuel post-treatment processes, a TBP/OK system is adopted to extract and purify uranium, plutonium and other nuclides. Military nuclear technology units such as atomic energy institute, nuclear power institute, 404 factory, 821 factory and the like can generate a certain amount of nuclear chemical TBP/OK organic waste liquid every year, along with the continuous increase of nuclear energy and peaceful utilization and military nuclear power platform scales, the amount of radioactive organic waste liquid can be rapidly increased, and the waste liquid is stored for a long time and has potential safety hazards such as corrosion, fire protection, radioactivity and the like, so that the inorganic safe treatment and disposal are urgently required. However, a safe and effective treatment process and matched equipment cannot be provided at home, and the introduction technology faces the problems of technical blockade, high cost and the like.
The TBP/OK organic waste liquid is subjected to inorganic treatment by adopting a certain technical means, and the method is an important method for realizing the aim of harmless treatment of the TBP/OK organic waste liquid. The inorganic treatment of organic waste liquid is a high and new technology, and the technology utilizes additives, promoters and the like to generate certain energy to destroy chemical bonds of pollutant molecules, so that the pollutant molecules are broken into small molecular substances, finally carbon in organic matters is converted into carbon dioxide, phosphorus and the like are converted into inorganic salts, and hydrogen and oxygen are converted into water, thereby eliminating pollutants.
In the inorganic treatment method of TBP/OK organic waste liquid, the direct combustion method is the earliest used and continues to be used up to now, but because the gasification temperature difference between TBP and kerosene is relatively large, the kerosene is gasified first and escapes in the high-temperature cracking process, and explosion is easy to occur when the kerosene is contacted with oxygen. In addition, the TBP contains phosphorus element, and the phosphorus can form volatile acid oxide during pyrolysis and is discharged along with gas phase, so that the pipeline of a subsequent system is strongly corroded; in the gas cooling process, phosphoric acid can be formed when meeting water vapor and is deposited in the system pipeline, so that equipment is damaged. An improved method is to add certain calcium compounds to the waste organic solvent and incinerate them together to neutralize the phosphoric acid. However, in the practical application process, the neutralization efficiency of phosphoric acid by calcium compounds is not high, and the process problem that the generated calcium pyrophosphate blocks pipelines is also caused, thereby increasing the difficulty of practical operation and providing more severe construction requirements for treatment equipment.
In order to reduce or eliminate the treatment pressure of the TBP/OK organic waste liquid, scientific and technological workers in various countries develop various treatment technologies of the TBP/OK organic waste liquid, which mainly comprise a pyrolysis incineration technology, a wet oxidation treatment technology, an absorption method, a cement curing method and the like. However, these methods have some disadvantages, as described below.
The pyrolysis incineration technology has the advantages that: the treatment is thorough, the ash content is stable, the tail gas amount is less, and the volatile nuclide is retained in the pyrolysis reactor and has less corrosion to equipment. Its disadvantages are: the reaction rate is slow, the tail gas contains carcinogenic poison such as dioxin, and the public acceptance degree is low.
The steam recombination technology has the advantages that: the filter is not easy to block, deposition of polyphosphoric acid is avoided, and the amount of secondary waste vaporized by the smoke is less. Its disadvantages are: the equipment requirement is high, and the tail gas needs to be treated.
The Fenton oxidation method has the advantages that: the reaction condition is mild, the technology is mature, and a movable treatment device can be established. Its disadvantages are: the reaction time is longer, and the amount of secondary waste liquid is larger.
The acid oxidation method has the advantages that: wide treatment range and low pressure. Its disadvantages are: the equipment has high corrosion resistance requirement and needs to treat tail gas. And the method is not engineered.
The supercritical water oxidation technology has the advantages that: the heat can be supplied by the oxidation of the organic matter to maintain the reaction, and the organic matter is completely oxidized into inorganic products. Its disadvantages are: difficult slag discharge and high requirements on treatment equipment. And the method is not engineered.
The electrochemical catalytic oxidation method has the advantages that: the tail gas treatment is simple. Its disadvantages are: high treatment cost and difficult industrialization. And the method is not engineered.
The absorption method has the advantages that: the process is simple. Its disadvantages are: the cost is high, and the treatment requirement can be met only by curing treatment. And the method is not engineered.
The cement curing method has the advantages that: the process is simple and the technology is mature. Its disadvantages are: the capacity increase is large, and the long-term performance of the cured body needs to be verified. And the method is not engineered.
The alkaline hydrolysis method has the advantages that: the technology is mature, the operation temperature is low, and the scale of the device is controllable. Its disadvantages are: the application range is narrow, and the generated secondary waste is complex and needs to be further treated.
It can be seen from the above various treatment methods that various TBP/OK organic waste liquid treatment technologies exist at present, but the technologies all have respective defects, and technologies such as pyrolysis incineration, steam recombination, acid oxidation and the like can generate intractable toxic and harmful tail gas in the TBP/OK treatment process, and high-performance tail gas treatment equipment needs to be arranged; a Fenton oxidation method, an alkaline hydrolysis method and the like can generate a large amount of secondary waste liquid with complex components, so that the treatment difficulty and the cost are increased; the reaction control conditions of the electrochemical catalytic oxidation method are complex, the operation is inconvenient and the power consumption is high; some of the absorbent production techniques used in the absorption method, which have high treatment efficiency, are still monopolized abroad, and in addition, secondary treatment of the by-products is required.
Although the national and various nuclear industry units continuously carry out the research on the treatment technology of the radioactive waste TBP/OK organic waste liquid for many years, no mature and available technology and complete equipment are developed so far, and the technology and the complete equipment are not matched with the national status of the nuclear industry. Therefore, the development of an efficient inorganic treatment technology for TBP/OK organic waste liquid and the construction of safe and simple treatment equipment are problems to be solved urgently in the development of the nuclear industry at present.
Disclosure of Invention
Aiming at the problems, the invention aims to provide a mineralization-oxidation treatment process of radioactive TBP/OK organic waste liquid, which realizes fixation of phosphorus element in TBP while efficiently cracking TBP/OK through the mineralization-oxidation process, reduces or eliminates the negative effect of the phosphorus element in the existing pyrolysis incineration process, and establishes an efficient mineralization phosphorus fixation technology of the TBP/OK organic waste liquid; meanwhile, organic components are completely converted into inorganic components at a lower temperature through a low-temperature oxidation treatment technology of mineralized gas, the mineralized solid phosphorus and inorganic oxidation treatment of the TBP/OK organic waste liquid is realized, and a process flow and complete equipment which are simple and convenient to operate, safe and controllable are constructed.
In order to realize the aim, the invention provides a mineralization-oxidation treatment process of radioactive TBP/OK organic waste liquid, which comprises the following steps:
the method comprises the following steps: adding different solid reaction base materials into the mineralization reactor and the oxidation reactor respectively; wherein the mineralization reactor is a first-stage reactor, and the oxidation reactor is a second-stage reactor;
step two: adding TBP/OK organic waste liquid into a first-stage reactor from a feed tank through a filling pump, wherein OK is gasified and enters the next-stage reaction, TBP is cracked into a micromolecule product under the action of a reaction substrate, and the generated gaseous product and OK enter a second-stage reactor together for reaction; the phosphorus-containing components are mineralized and fixed by the reaction base material to form a solid product with stable property, and reaction residues are periodically discharged into a waste steel drum and then packaged to be used as radioactive solid waste for treatment;
step three: gas products generated by the first-stage reactor enter a second-stage reactor, mineralized gas is further oxidized by the reaction substrate and converted into carbon dioxide and water, wherein the mineralized gas is small molecular organic products generated by cracking gasified OK and TBP;
step four: the gas generated in the secondary reactor sequentially passes through a heat exchanger cooling filter, a dust removal filter and a high-efficiency filter to remove entrained particles, is pumped out by an induced draft fan, is connected with an exhaust pipeline of the nuclear facility, and is safely discharged.
Further, the TBP/OK mass in the first-stage reactor is not more than 1/10 of the solidification reaction substrate, and the feeding is carried out after the reaction is completed, wherein the feeding mode comprises an intermittent quantitative mode or a continuous metering mode, and the metering mode is carried out in a constant volume, constant mass or pump metering mode.
Further, the solid reaction substrate comprises a mixture formed by any one or more metal oxides, wherein the reaction substrate added in the first-stage reactor is used for catalytic cracking of TBP and mineralized fixation of phosphorus-containing components after cracking, and the reaction substrate added in the second-stage reactor is used as a catalyst and an oxidant in the oxidation process of mineralized gas.
Furthermore, in the reaction process, inert gas is introduced into the first-stage reactor and the second-stage reactor to be used as protective gas.
Furthermore, a regeneration gas tank is connected to the gas inlet of the secondary reactor, and when the reactivity of the solid base material is reduced to below 40%, the feeding is stopped and the regeneration gas is introduced, so that the activity of the solid base material is regenerated on line.
Furthermore, gas outlets of the first-stage reactor and the second-stage reactor are connected with gas online analyzers, and functions of the gas online analyzers are flexibly configured according to the purpose of monitoring gas components.
Furthermore, the rear end of the high-efficiency filter is connected with an induced draft fan, an outlet of the induced draft fan is connected with an exhaust system of the radioactive waste treatment facility, and a beta counter is connected between the induced draft fan and the exhaust system.
The technical principle is as follows:
the TBP/OK organic waste liquid firstly enters a primary reactor to carry out TBP catalytic cracking and phosphorus fixation reaction, and the reaction mechanism is as follows:
(C4H9O)3PO+MexOy→Me2x(P2O7)y+CaHbOc↑
in the first-stage reactor, OK components are volatilized at a lower temperature, TBP and a reaction substrate react at a certain temperature to generate pyrophosphate (solid state) and organic matters (gaseous state), and the volatilized OK components and gas-phase organic products generated by TBP cracking enter a second-stage reactor.
The mineralized gas (small molecule organic products from cracking of gasified OK and TBP) enters a secondary reactor, and the reaction mechanism is as follows:
CaHbOc+MexOy→MexOy-r+CO2+H2O
the mineralized gas entering the secondary reactor reacts with the reaction substrate under a certain temperature condition to generate oxidation-reduction reaction, and carbon dioxide and water are generated.
In summary, compared with the prior art, the invention has the following beneficial effects:
(1) the treatment process realizes mineralization fixation of phosphorus element while efficiently cracking TBP, reduces or eliminates negative influence of phosphorus element in the existing pyrolysis incineration process, and establishes an efficient mineralization phosphorus fixation technology for TBP organic waste liquid;
(2) the invention realizes the phosphorus fixation and inorganic treatment of the TBP/OK organic waste liquid by coupling the mineralization phosphorus fixation technology and the low-temperature oxidation technology, and constructs a process flow and complete equipment which are simple and convenient to operate, safe and controllable;
(3) the treatment process has the advantages of low energy consumption, high purification efficiency, no secondary pollution and high adaptability.
Drawings
FIG. 1 is a process flow diagram of an inorganic phosphorus fixation process for radioactive TBP/OK organic waste liquid in the invention.
Detailed Description
All features disclosed in this specification may be combined in any combination, except features and/or steps that are mutually exclusive.
In order to make the technical solutions of the present invention better understood by those skilled in the art, the present invention is further described in detail with reference to fig. 1 and the specific embodiments.
Example 1
As shown in fig. 1, a mineralization-oxidation treatment process of radioactive TBP/OK organic waste liquid comprises the following steps:
the method comprises the following steps: adding different solid reaction base materials into the mineralization reactor and the oxidation reactor respectively; wherein the mineralization reactor is a first-stage reactor, and the oxidation reactor is a second-stage reactor;
step two: adding TBP/OK organic waste liquid into a first-stage reactor from a feed tank through a filling pump, wherein OK is gasified and enters the next-stage reaction, TBP is cracked into a micromolecule product under the action of a reaction substrate, and the generated gaseous product and OK enter a second-stage reactor together for reaction; the phosphorus-containing components are mineralized and fixed by the reaction base material to form a solid product with stable property, and reaction residues are periodically discharged into a waste steel drum and then packaged to be used as radioactive solid waste for treatment;
step three: the mineralized gas generated by the first-stage reactor enters a second-stage reactor, the mineralized gas is further oxidized by the reaction substrate and is converted into carbon dioxide and water, wherein the mineralized gas is a small molecular organic product generated by cracking gasified OK and TBP;
step four: the gas generated in the secondary reactor sequentially passes through a heat exchanger cooling filter, a dust removal filter and a high-efficiency filter to remove entrained particles, is pumped out by an induced draft fan, is connected with an exhaust pipeline of the nuclear facility, and is safely discharged.
On the basis of basic scientific research, the invention designs and constructs a waste TBP/OK waste liquid mineralization-oxidation pilot plant, performs cold and hot tests, tests the technological conditions and mechanisms of the multifunctional catalyst catalysis and phosphorus fixation, optimizes the technological parameters of catalytic reaction, and lays a solid technical foundation for the development of engineering equipment for treating the waste TBP through fuel conversion and purification.
The TBP/OK organic waste liquid firstly enters a primary reactor to carry out TBP catalytic phosphorus fixation reaction, and the reaction mechanism is as follows:
(C4H9O)3PO+MexOy→Me2x(P2O7)y+CaHbOc↑
in the first-stage reactor, OK components are volatilized at a lower temperature, TBP and a reaction substrate react at a certain temperature to generate pyrophosphate (solid state) and organic matters (gaseous state), and the volatilized OK components and gas-phase organic products generated by TBP cracking enter a second-stage reactor.
The mineralized gas (small molecule organic products from cracking of gasified OK and TBP) enters a secondary reactor, and the reaction mechanism is as follows:
CaHbOc+MexOy→MexOy-r+CO2+H2O
the mineralized gas entering the secondary reactor reacts with the reaction substrate under a certain temperature condition to generate oxidation-reduction reaction, and carbon dioxide and water are generated.
The TBP/OK mass in the first-stage reactor is not more than 1/10 of the solidification reaction substrate, and the feeding is carried out after the reaction is completed, wherein the feeding mode comprises a batch quantitative mode or a continuous metering mode, and the metering mode adopts a constant volume, constant mass or pump metering mode.
The solid reaction base material comprises a mixture formed by any one or more metal oxides, wherein the reaction base material added in the first-stage reactor is used for catalytic cracking of TBP and mineralized fixation of phosphorus-containing components after cracking, and the reaction base material added in the second-stage reactor is used as a catalyst and an oxidant in the oxidation process of mineralized gas.
In the reaction process, inert gas is introduced into the first-stage reactor and the second-stage reactor as protective gas.
The gas inlet of the secondary reactor is connected with a regeneration gas tank, and when the reaction activity of the solid base material is reduced to below 40%, the feeding is stopped and the regeneration gas is introduced, so that the activity of the solid base material is regenerated on line.
It should be noted that the gas outlets of the first-stage reactor and the second-stage reactor are both connected with a gas online analyzer, and the functions of the gas online analyzer are flexibly configured according to the purpose of monitoring gas components.
The rear end of the high-efficiency filter is connected with an induced draft fan, an outlet of the induced draft fan is connected with an exhaust system of the radioactive waste treatment facility, and a beta counter is connected between the induced draft fan and the exhaust system.
The effect is detected as follows:
(1) the processing capacity of the device is 500 mL-1000 mL/h;
(2) the immobilization efficiency of total phosphorus in TBP is more than or equal to 95 percent;
(3) the mineralization efficiency of organic components in the TBP/OK organic waste liquid is more than or equal to 99 percent.
The above-mentioned embodiments only express the specific embodiments of the present application, and the description thereof is more specific and detailed, but not construed as limiting the scope of the present application. It should be noted that, for those skilled in the art, without departing from the technical idea of the present application, several changes and modifications can be made, which are all within the protection scope of the present application.
Claims (7)
1. A mineralization-oxidation treatment process for radioactive TBP/OK organic waste liquid is characterized by comprising the following steps:
the method comprises the following steps: adding different solid reaction base materials into the mineralization reactor and the oxidation reactor respectively; wherein the mineralization reactor is a first-stage reactor, and the oxidation reactor is a second-stage reactor;
step two: adding TBP/OK organic waste liquid into a first-stage reactor from a feed tank through a filling pump, wherein OK is gasified and enters the next-stage reaction, TBP is cracked into a micromolecule product under the action of a reaction substrate, and the generated gaseous product and OK enter a second-stage reactor together for reaction; the phosphorus-containing components are mineralized and fixed by the reaction base material to form a solid product with stable property, and reaction residues are periodically discharged into a waste steel drum and then packaged to be used as radioactive solid waste for treatment;
step three: gas products generated by the first-stage reactor enter a second-stage reactor, mineralized gas is further oxidized by the reaction substrate and converted into carbon dioxide and water, wherein the mineralized gas is small molecular organic products generated by cracking gasified OK and TBP;
step four: the gas generated in the secondary reactor sequentially passes through a heat exchanger cooling filter, a dust removal filter and a high-efficiency filter to remove entrained particles, is pumped out by an induced draft fan, is connected with an exhaust pipeline of the nuclear facility, and is safely discharged.
2. The mineralization-oxidation treatment process of radioactive TBP/OK organic waste liquid as claimed in claim 1, wherein TBP/OK mass in said primary reactor is not more than 1/10 of solidification reaction substrate, feeding is carried out after reaction is completed, feeding mode comprises intermittent quantitative mode or continuous metering mode, and metering mode is constant volume, constant mass or pump metering mode.
3. The mineralization-oxidation treatment process of the radioactive TBP/OK organic waste liquid as claimed in claim 1, wherein the solid reaction substrate comprises a mixture of any one or more metal oxides, wherein the reaction substrate added in the first stage reactor is used for catalytic cracking of TBP and mineralized immobilization of phosphorus-containing components after cracking, and the reaction substrate added in the second stage reactor is used as a catalyst and an oxidant in the mineralized gas oxidation process.
4. The mineralization-oxidation treatment process of radioactive TBP/OK organic waste liquid as claimed in claim 1, wherein inert gas is introduced into the primary reactor and the secondary reactor as shielding gas during the reaction process.
5. The mineralization-oxidation treatment process of radioactive TBP/OK organic waste liquid as claimed in claim 1, wherein a regeneration gas tank is connected to the gas inlet of the secondary reactor, and when the reactivity of the solid substrate is reduced to below 40%, the feeding is stopped and the regeneration gas is introduced to regenerate the activity of the solid substrate on line.
6. The mineralization-oxidation treatment process of radioactive TBP/OK organic waste liquid as claimed in claim 1, wherein gas outlets of the first stage reactor and the second stage reactor are connected with gas on-line analyzers, and functions of the gas on-line analyzers are flexibly configured according to gas component monitoring purposes.
7. The mineralization-oxidation treatment process of the radioactive TBP/OK organic waste liquid as claimed in claim 1, wherein a draught fan is connected to the rear end of the high efficiency filter, an outlet of the draught fan is connected to an exhaust system of a radioactive waste treatment facility, and a beta counter is connected between the draught fan and the exhaust system.
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