CN107658038B - Radiological techniques treatment of wastes produced method - Google Patents
Radiological techniques treatment of wastes produced method Download PDFInfo
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- CN107658038B CN107658038B CN201710762191.9A CN201710762191A CN107658038B CN 107658038 B CN107658038 B CN 107658038B CN 201710762191 A CN201710762191 A CN 201710762191A CN 107658038 B CN107658038 B CN 107658038B
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- pva
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- wastes produced
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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
- G21F9/28—Treating solids
- G21F9/30—Processing
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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
Abstract
The present invention provides a kind of radiological techniques treatment of wastes produced method.The processing method at least includes the following steps: surface contact agent dose rate < 2mSv/h PVA product waste material that nuclear power plant generates being placed in water and is heated, PVA product waste material is dissolved, obtains PVA aqueous solution；Fenton reagent is added into PVA aqueous solution, makes PVA that oxidative degradation occur, obtains degradation solution；Degradation solution is filtered processing, the insoluble matter that partial size is greater than 0.25 μm is filtered out, and heated oxide processing is carried out to filtrate, makes activity concentration≤1MBq/m of filtrate3, COD≤100mg/L；BOD≤30mg, collects the gas of heated oxide processing discharge, carries out catalytic oxidation treatment to gas.Treatment method simple process, less energy consumption are beneficial to energy conservation emission reduction and protection environment, avoid the accumulation of PVA product waste material in nuclear power plant, and obtained product is environmentally friendly.
Description
Technical field
The invention belongs to nuclear pollution waste processing arts, and in particular to a kind of radiological techniques treatment of wastes produced side
Method.
Background technique
As nuclear technology utilizes, the fast development of nuclear power station, nuclear power plant produces largely during operation and refueling outage
Technology waste.These technology wastes mainly apply maintenance protective articles, such as plastic cloth/bag plastic products.According to original
It designs these technology wastes and all individually carries out barrelling compression, increase solid waste volume and cost of disposal.It minimizes and considers from waste, this
The processing incineration technology of a little radioactive wastes is maximally efficient, but domestic at present in fortune nuclear power plant introduction incineration technology and its difficulty.
The control zone plastic products in current each nuclear power base are all made of PE product, under the superpressure treatment process in power station, deposit
In compression rebound effect, for existing treatment process, there are biggish restrictions, even if using superpressure technique, volume reduction ratio is also only
30%.And the volume reduction ratio of PVA product can achieve 10000:1, therefore PVA product is for that can efficiently reduce nuclear power in nuclear power plant
The accumulation and disposition quantity of solid radioactive technology waste in factory's operational process, this makes PVA attractive as one
Realize the practical technique that radioactive waste minimizes.In 6.1 chapters and sections of IAEA public publication " IAEA-WMDB-ST-3 ",
EPRI (American Electric Power research association) recommends to realize the volume reduction of solid radioactive waste using PVA material in nuclear power field.That
Accordingly, it is desirable to propose a kind of PVA biodegrading process discarded suitable for nuclear power plant.
Summary of the invention
The shielding waste material generated for current nuclear power plant is more and more, and cannot be according to conventional side due to radioactivity
The problems such as method processing, the present invention provides a kind of radiological techniques treatment of wastes produced methods.
In order to achieve the above-mentioned object of the invention, the technical solution of the embodiment of the present invention is as follows:
A kind of radiological techniques treatment of wastes produced method, at least includes the following steps:
Surface contact agent dose rate < 2mSv/h PVA product waste material that nuclear power plant generates is placed in water and is heated,
PVA product waste material is hydrolyzed, PVA aqueous solution is obtained；
Fenton reagent is added into the PVA aqueous solution, makes PVA that oxidative degradation occur, obtains degradation solution；
The degradation solution is filtered processing, filters out the insoluble matter that partial size is greater than 0.25 μm, and heat to filtrate
Oxidation processes make activity concentration≤1MBq/m of the filtrate3, discharge standard and COD≤100mg/L, BOD≤
30mg；The gas for collecting the heated oxide processing discharge, carries out catalytic oxidation treatment to the gas.
Compared with the existing technology, radiological techniques treatment of wastes produced method provided by the invention, specifically to PVA shielding
It is handled, realizes the degradation of surface contact agent dose rate < 2mSv/h PVA product waste material, avoid the heap of PVA product waste material
Product, and catabolite is environmentally friendly, waste liquid activity concentration reaches national emission standard；COD and BOD value reaches state
Family's discharge mark；The biodegrading process simple process, less energy consumption are beneficial to energy conservation emission reduction and protection environment.
Specific embodiment
In order to make the objectives, technical solutions, and advantages of the present invention clearer, with reference to embodiments, to the present invention
It is further elaborated.It should be appreciated that the specific embodiments described herein are merely illustrative of the present invention, it is not used to
Limit the present invention.
Present example provides a kind of radiological techniques treatment of wastes produced method.The processing method includes at least following step
It is rapid:
Surface contact agent dose rate < 2mSv/h PVA product waste material that nuclear power plant generates is placed in water and is heated,
PVA product waste material is hydrolyzed, PVA aqueous solution is obtained；
Fenton reagent is added into the PVA aqueous solution, makes PVA that oxidative degradation occur, obtains degradation solution；
The degradation solution is filtered processing, filters out the insoluble matter that partial size is greater than 0.25 μm, and heat to filtrate
Oxidation processes make activity concentration≤1MBq/m of the filtrate3, COD≤100mg/L, BOD≤30mg；Described in collection
The gas of heated oxide processing discharge, carries out catalytic oxidation treatment to the gas.
Explanation is further explained to the biodegrading process below.
Using the above-mentioned radiological techniques waste treatment method of the present invention to being at the PVA waste generated to nuclear power plant
Reason, should meet PVA product waste material be halogen-free, the nuclear power plants such as sulfate radical disabling chemical component.
Before being handled, PVA product waste material should be sorted, it is impossible to degradation and surface contact agent dose rate >=
The sorting of 2mSv/h removes, because being unable to satisfy national emission standard after degradation as surface contact agent dose rate >=2mSv/h, because
This, exceeded PVA product waste material needs otherwise processed.
By heat treatment, so that PVA product waste material dissolves, the dissolved aqueous solution of PVA is formed, so as to further
Carry out Fenton degradation reaction.
Preferably, the temperature of the heat treatment be 100 DEG C~150 DEG C, by the temperature of heating for dissolving be set to 100 DEG C~
150 DEG C, the PVA product waste material for being primarily due to nuclear power plant's generation not can guarantee from different producers and different models
Solution temperature is completely the same, when temperature is more than 100 DEG C, it can be ensured that the PVA of different model different manufacturers can occur completely
Dissolution, and if it exceeds 150 DEG C, then it will increase energy consumption.
Water for dissolving PVA is nuclear power plant's demineralized water.
In order to facilitate processing, material shifts the usage amount of workload and equipment in reduction processing, directly in PVA aqueous solution
Middle addition Fenton (Fenton) reagent.
Preferably, Fenton reagent of the present invention is the hydrogen peroxide comprising ferrous ion.Include ferrous ion
PVA can be degraded to the weak organic acid solution of small molecular organic acid and intermediary by hydrogen peroxide.
Preferably, the temperature of Fenton's reaction is 90 DEG C~110 DEG C, at such a temperature, not only improves the degradation of PVA, and keep away
Exempt to cause hydrogen peroxide to boil because temperature is excessively high and volatilize.
Generally, during Fenton's reaction, according to mass ratio, the inventory of hydrogen peroxide is slightly in excess in PVA, to ensure
PVA is degraded completely.
Preferably, according to mass ratio, feed ratio PVA: hydrogen peroxide=5:6.
Processing is filtered to the solution that Fenton's reaction is degraded, filters out the insoluble matter that partial size is greater than 0.25 μm, and right
Insoluble matter is collected, detects radionuclide amount, when radionuclide amount reaches national emission standard, Ke Yipai
It puts, if unqualified, carries out other processing after label.
Heated oxide processing is carried out to the filtrate obtained after filtering, heated oxide processing mainly generates Fenton's reaction
Weak organic acid further aoxidizes, it is made to be converted into carbon dioxide and water and liquid oxygen compound, with reduce the COD in filtrate and
BOD value reaches the standard of discharge.
Preferably, the temperature of the heated oxide processing is 600 DEG C~700 DEG C, at such a temperature, is able to achieve weak organic acid
Complete oxidation, while production energy consumption can be reduced as far as possible.
When heated oxide processing, since temperature is relatively high, generation carbon monoxide, carbon dioxide and vapor, and an oxygen
Change carbon to be directly discharged to will cause air pollution in air, it is therefore desirable to which the hot gas for generating heated oxide processing is received
Collection, and catalytic oxidation treatment is carried out, carbon dioxide is converted by carbon monoxide therein, then cooling hot gas, so that water steams
Gas condenses, and discharges after detecting environmental sound without solidifying gas.
Preferably, the catalysis oxidation is using the alloy of noble metal or noble metal as catalyst.
It is further preferred that the catalyst is platinum catalyst or platinum plating metallic catalyst.
Preferably, the temperature of catalysis oxidation is 550 DEG C~650 DEG C.Catalytic activity highest in the temperature range.
Radiological techniques treatment of wastes produced method provided by the invention realizes surface contact agent dose rate < 2mSv/h PVA
The degradation of product waste material avoids the accumulation of PVA product waste material in nuclear power plant, and catabolite is environmentally friendly, radioactivity
Activity concentration≤1MBq/m3, COD and BOD value reach country discharge mark；The processing method simple process, less energy consumption, are conducive to save
It can emission reduction and protection environment.
More effectively to illustrate technical solution of the present invention, illustrate that the embodiment of the present invention is radiated below by multiple embodiments
Property technology treatment of wastes produced method.
Embodiment 1
A kind of radiological techniques treatment of wastes produced method, comprising the following steps:
(1) the PVA protective articles generated during nuclear power plant's overhaul be collected, transported, sorted and surface exposure dose
Rate etc. is detected, and using the surface contact agent dose rate of 2mSv/h as classification point, is divided into surface contact agent dose rate >=2mSv/h
PVA product waste material and surface contact agent dose rate < 2mSv/h PVA product waste material；
(2) surface contact agent dose rate < 2mSv/h PVA product waste material investment is held in the device of tap water, and to it
It is heated, heating temperature is 100 DEG C, stirring, until PVA is completely dissolved in water；
(3) be added in Xiang Suoshu PVA solution include ferrous ion hydrogen peroxide, wherein PVA and hydrogen peroxide feed intake
Mass ratio is 5:6, Fenton's reaction is carried out, so that PVA is degraded to the weak organic acid solution of small molecular organic acid and intermediary；
(4) it is cooled to room temperature to solution obtained in step (3), carries out that processing is filtered for multiple times, filter out partial size and be greater than
0.25 μm of insoluble particles object, and collect and detect obtained insoluble particles object；
(5) heated oxide processing is carried out to filtrate, is heated to 600 DEG C, and collect the gas generated during heated oxide
And vapor, gas and vapor are subjected to catalysis oxidation together, using platinum group metal as catalyst, the temperature of catalysis oxidation
It is 600 DEG C, after catalysis oxidation, condensation process is carried out to gas and vapor, not solidifying gas, handled simultaneously by high efficiency particulate air filter
After detection is qualified, discharged into air.Heated oxide treated filtered fluid, through detecting, activity concentration is about
0.8MBq/m3, COD is about 86mg/L, and BOD is about 18mg, meets discharge standard.
Embodiment 2
A kind of radiological techniques treatment of wastes produced method, comprising the following steps:
(1) the PVA protective articles generated during nuclear power plant's overhaul be collected, transported, sorted and surface exposure dose
Rate etc. is detected, and using the surface contact agent dose rate of 2mSv/h as classification point, is divided into surface contact agent dose rate >=2mSv/h
PVA product waste material and surface contact agent dose rate < 2mSv/h PVA product waste material；
(2) surface contact agent dose rate < 2mSv/h PVA product waste material investment is held in the device of tap water, and to it
It is heated, heating temperature is 150 DEG C, stirring, until PVA is completely dissolved in water；
(3) be added in Xiang Suoshu PVA solution include ferrous ion hydrogen peroxide, wherein PVA and hydrogen peroxide feed intake
Mass ratio is 5:6, Fenton's reaction is carried out, so that PVA is degraded to the weak organic acid solution of small molecular organic acid and intermediary；
(4) it is cooled to room temperature to solution obtained in step (3), carries out that processing is filtered for multiple times, filter out partial size and be greater than
0.25 μm of insoluble particles object, and collect and detect obtained insoluble particles object；
(5) heated oxide processing is carried out to filtrate, is heated to 700 DEG C, and collect the gas generated during heated oxide
And vapor, gas and vapor are subjected to catalysis oxidation together, using platinum group metal as catalyst, the temperature of catalysis oxidation
It is 600 DEG C, after catalysis oxidation, condensation process is carried out to gas and vapor, not solidifying gas, handled simultaneously by high efficiency particulate air filter
After detection is qualified, discharged into air.Heated oxide treated filtered fluid, through detecting, activity concentration is about
0.5MBq/m3, COD is about 72mg/L, and BOD is about 25mg, meets discharge standard.
Embodiment 3
A kind of radiological techniques treatment of wastes produced method, comprising the following steps:
(1) the PVA protective articles generated during nuclear power plant's overhaul be collected, transported, sorted and surface exposure dose
Rate etc. is detected, and using the surface contact agent dose rate of 2mSv/h as classification point, is divided into surface contact agent dose rate >=2mSv/h
PVA product waste material and surface contact agent dose rate < 2mSv/h PVA product waste material；
(2) surface contact agent dose rate < 2mSv/h PVA product waste material investment is held in the device of tap water, and to it
It is heated, heating temperature is 130 DEG C, stirring, until PVA is completely dissolved in water；
(3) be added in Xiang Suoshu PVA solution include ferrous ion hydrogen peroxide, wherein PVA and hydrogen peroxide feed intake
Mass ratio is 5:6, Fenton's reaction is carried out, so that PVA is degraded to the weak organic acid solution of small molecular organic acid and intermediary；
(4) it is cooled to room temperature to solution obtained in step (3), carries out that processing is filtered for multiple times, filter out partial size and be greater than
0.25 μm of insoluble particles object, and collect and detect obtained insoluble particles object；
(5) heated oxide processing is carried out to filtrate, is heated to 650 DEG C, and collect the gas generated during heated oxide
And vapor, gas and vapor are subjected to catalysis oxidation together, using platinum group metal as catalyst, the temperature of catalysis oxidation
It is 600 DEG C, after catalysis oxidation, condensation process is carried out to gas and vapor, not solidifying gas, handled simultaneously by high efficiency particulate air filter
After detection is qualified, discharged into air.Heated oxide treated filtered fluid, through detecting, activity concentration is about
0.6MBq/m3, COD is about 83mg/L, and BOD is about 21mg, meets discharge standard.
The foregoing is merely illustrative of the preferred embodiments of the present invention, is not intended to limit the invention, all in essence of the invention
Made any modifications, equivalent replacements, and improvements etc. within mind and principle should all include within protection scope of the present invention.
Claims (6)
1. a kind of radiological techniques treatment of wastes produced method, it is characterised in that: at least include the following steps:
Surface contact agent dose rate < 2mSv/h PVA product waste material that nuclear power plant generates is placed in water and is heated, is made
PVA product waste material dissolves, and obtains the dissolved aqueous solution of PVA；
Fenton reagent is added into the PVA aqueous solution, makes PVA that oxidative degradation occur, obtains degradation solution；
Processing is filtered to the degradation solution, filters out the insoluble matter that partial size is greater than 0.25 μm, and heated oxide is carried out to filtrate
Processing, makes activity concentration≤1MBq/m of the filtrate3, and COD≤100mg/L, BOD≤30mg；Collect described add
The gas of thermal oxidation discharge carries out catalytic oxidation treatment to the gas；
The temperature of the heated oxide processing is 600 DEG C~700 DEG C；The temperature of the catalysis oxidation is 550 DEG C~650 DEG C.
2. radiological techniques treatment of wastes produced method as described in claim 1, it is characterised in that: the temperature of the heat treatment
It is 100 DEG C~150 DEG C.
3. radiological techniques treatment of wastes produced method as described in claim 1, it is characterised in that: the catalysis oxidation is using expensive
The alloy of metal or noble metal is as catalyst.
4. radiological techniques treatment of wastes produced method as claimed in claim 3, it is characterised in that: the catalyst is urged for platinum
Agent or platinum plating metallic catalyst.
5. radiological techniques treatment of wastes produced method as described in claim 1, it is characterised in that: need to carry out the catalysis oxygen
The gas for changing processing is carbon monoxide.
6. radiological techniques treatment of wastes produced method as described in claim 1, it is characterised in that: the heated oxide processing
It afterwards, further include that the vapor generated to heated oxide processing carries out condensation process.
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Families Citing this family (4)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN113096843B (en) * | 2019-12-23 | 2024-04-23 | 中广核研究院有限公司 | Method for treating radioactive solid waste |
| CN112820438A (en) * | 2020-04-30 | 2021-05-18 | 东部技术公司 | Chemical oxidation treatment process of PVA waste treatment system |
| CN112547754A (en) * | 2020-11-05 | 2021-03-26 | 江苏景泰石油化工装备有限公司 | Control method and system of waste treatment system, readable storage medium and programmable controller |
| CN112908508B (en) * | 2021-01-12 | 2022-11-04 | 中国工程物理研究院材料研究所 | Method for treating radioactive analysis waste liquid by one-step method |
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| JPS6113195A (en) * | 1984-06-28 | 1986-01-21 | 住友化学工業株式会社 | Method of treating radioactive waste water |
| CN102754167A (en) * | 2009-11-17 | 2012-10-24 | 汉纳检查及工程有限公司 | Disposal and decontamination of radioactive polyvinyl alcohol products |
| CN106251924A (en) * | 2016-01-21 | 2016-12-21 | 青岛天和清原科技有限公司 | Supercritical water oxidation processes the method for PVA polymeric material |
| CN106875995A (en) * | 2017-01-20 | 2017-06-20 | 魏家奎 | A kind of method for purifying the degradable PVA products of low-activity in disposal |
Family Cites Families (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2005031757A1 (en) * | 2003-09-23 | 2005-04-07 | Microtek Medical Holdings, Inc. | Strippable pva coatings and methods of making and using the same |
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- 2017-08-30 CN CN201710762191.9A patent/CN107658038B/en active Active
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS6113195A (en) * | 1984-06-28 | 1986-01-21 | 住友化学工業株式会社 | Method of treating radioactive waste water |
| CN102754167A (en) * | 2009-11-17 | 2012-10-24 | 汉纳检查及工程有限公司 | Disposal and decontamination of radioactive polyvinyl alcohol products |
| CN106251924A (en) * | 2016-01-21 | 2016-12-21 | 青岛天和清原科技有限公司 | Supercritical water oxidation processes the method for PVA polymeric material |
| CN106875995A (en) * | 2017-01-20 | 2017-06-20 | 魏家奎 | A kind of method for purifying the degradable PVA products of low-activity in disposal |
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