CN108560003A - A kind of metal surface radioactive pollution detergent and its application method - Google Patents
A kind of metal surface radioactive pollution detergent and its application method Download PDFInfo
- Publication number
- CN108560003A CN108560003A CN201810015754.2A CN201810015754A CN108560003A CN 108560003 A CN108560003 A CN 108560003A CN 201810015754 A CN201810015754 A CN 201810015754A CN 108560003 A CN108560003 A CN 108560003A
- Authority
- CN
- China
- Prior art keywords
- detergent
- decontamination
- aqueous solution
- metal surface
- radioactive pollution
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- 239000003599 detergent Substances 0.000 title claims abstract description 47
- 238000000034 method Methods 0.000 title claims abstract description 38
- 238000003904 radioactive pollution Methods 0.000 title claims abstract description 18
- 229910052751 metal Inorganic materials 0.000 title claims abstract description 13
- 239000002184 metal Substances 0.000 title claims abstract description 13
- 239000008139 complexing agent Substances 0.000 claims abstract description 14
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 13
- 239000007800 oxidant agent Substances 0.000 claims abstract description 12
- 239000007864 aqueous solution Substances 0.000 claims abstract description 11
- 230000001590 oxidative effect Effects 0.000 claims abstract description 11
- 239000002253 acid Substances 0.000 claims abstract description 10
- 239000007788 liquid Substances 0.000 claims abstract description 10
- 239000000126 substance Substances 0.000 claims abstract description 9
- 239000000203 mixture Substances 0.000 claims abstract description 8
- 238000001802 infusion Methods 0.000 claims abstract description 5
- 150000001449 anionic compounds Chemical class 0.000 claims abstract description 3
- 150000001768 cations Chemical class 0.000 claims abstract description 3
- 150000001875 compounds Chemical class 0.000 claims abstract description 3
- 229910001412 inorganic anion Inorganic materials 0.000 claims abstract description 3
- WQYVRQLZKVEZGA-UHFFFAOYSA-N hypochlorite Chemical compound Cl[O-] WQYVRQLZKVEZGA-UHFFFAOYSA-N 0.000 claims description 8
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 claims description 4
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 claims description 3
- 239000008367 deionised water Substances 0.000 claims description 3
- 229910021641 deionized water Inorganic materials 0.000 claims description 3
- 238000003860 storage Methods 0.000 claims description 3
- -1 highly basic Substances 0.000 claims description 2
- 239000003446 ligand Substances 0.000 claims description 2
- 239000006199 nebulizer Substances 0.000 claims description 2
- 239000011780 sodium chloride Substances 0.000 claims description 2
- SUKJFIGYRHOWBL-UHFFFAOYSA-N sodium hypochlorite Chemical group [Na+].Cl[O-] SUKJFIGYRHOWBL-UHFFFAOYSA-N 0.000 claims description 2
- 150000001805 chlorine compounds Chemical class 0.000 claims 1
- 238000005202 decontamination Methods 0.000 abstract description 38
- 230000003588 decontaminative effect Effects 0.000 abstract description 30
- 238000005530 etching Methods 0.000 abstract description 11
- 239000002699 waste material Substances 0.000 abstract description 9
- 230000002285 radioactive effect Effects 0.000 abstract description 8
- 239000003595 mist Substances 0.000 abstract description 5
- 230000036632 reaction speed Effects 0.000 abstract description 3
- 239000003344 environmental pollutant Substances 0.000 abstract description 2
- 239000002360 explosive Substances 0.000 abstract description 2
- 231100000719 pollutant Toxicity 0.000 abstract description 2
- 229910000619 316 stainless steel Inorganic materials 0.000 description 8
- 238000005516 engineering process Methods 0.000 description 7
- 238000011109 contamination Methods 0.000 description 6
- 238000005260 corrosion Methods 0.000 description 6
- 230000007797 corrosion Effects 0.000 description 6
- 238000009472 formulation Methods 0.000 description 5
- 238000012360 testing method Methods 0.000 description 5
- 239000007789 gas Substances 0.000 description 4
- 238000012545 processing Methods 0.000 description 4
- 239000000941 radioactive substance Substances 0.000 description 4
- 239000007921 spray Substances 0.000 description 4
- 239000000243 solution Substances 0.000 description 3
- 239000000758 substrate Substances 0.000 description 3
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 2
- 241000209094 Oryza Species 0.000 description 2
- 235000007164 Oryza sativa Nutrition 0.000 description 2
- 229910052770 Uranium Inorganic materials 0.000 description 2
- 238000006243 chemical reaction Methods 0.000 description 2
- 239000003795 chemical substances by application Substances 0.000 description 2
- 239000001257 hydrogen Substances 0.000 description 2
- 229910052739 hydrogen Inorganic materials 0.000 description 2
- 235000009566 rice Nutrition 0.000 description 2
- JFALSRSLKYAFGM-UHFFFAOYSA-N uranium(0) Chemical group [U] JFALSRSLKYAFGM-UHFFFAOYSA-N 0.000 description 2
- 229910000667 (NH4)2Ce(NO3)6 Inorganic materials 0.000 description 1
- 108091092584 GDNA Proteins 0.000 description 1
- 229910052792 caesium Inorganic materials 0.000 description 1
- TVFDJXOCXUVLDH-UHFFFAOYSA-N caesium atom Chemical compound [Cs] TVFDJXOCXUVLDH-UHFFFAOYSA-N 0.000 description 1
- 239000004568 cement Substances 0.000 description 1
- 238000013461 design Methods 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 230000005611 electricity Effects 0.000 description 1
- 238000005868 electrolysis reaction Methods 0.000 description 1
- 238000006056 electrooxidation reaction Methods 0.000 description 1
- 230000008030 elimination Effects 0.000 description 1
- 238000003379 elimination reaction Methods 0.000 description 1
- 238000004880 explosion Methods 0.000 description 1
- 238000002386 leaching Methods 0.000 description 1
- 239000002925 low-level radioactive waste Substances 0.000 description 1
- 238000012423 maintenance Methods 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- NICDRCVJGXLKSF-UHFFFAOYSA-N nitric acid;trihydrochloride Chemical compound Cl.Cl.Cl.O[N+]([O-])=O NICDRCVJGXLKSF-UHFFFAOYSA-N 0.000 description 1
- 230000005855 radiation Effects 0.000 description 1
- 239000002354 radioactive wastewater Substances 0.000 description 1
- 238000007789 sealing Methods 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 238000007711 solidification Methods 0.000 description 1
- 230000008023 solidification Effects 0.000 description 1
- 238000005507 spraying Methods 0.000 description 1
- 239000002344 surface layer Substances 0.000 description 1
- 238000002604 ultrasonography Methods 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23G—CLEANING OR DE-GREASING OF METALLIC MATERIAL BY CHEMICAL METHODS OTHER THAN ELECTROLYSIS
- C23G1/00—Cleaning or pickling metallic material with solutions or molten salts
- C23G1/02—Cleaning or pickling metallic material with solutions or molten salts with acid solutions
Landscapes
- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- General Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Mechanical Engineering (AREA)
- Metallurgy (AREA)
- Organic Chemistry (AREA)
- Detergent Compositions (AREA)
- Cleaning And De-Greasing Of Metallic Materials By Chemical Methods (AREA)
Abstract
The present invention relates to chemical field, in particular to a kind of metal surface radioactive pollution detergent and its application methods, it is characterised in that：The detergent is oxidant and the isometric mixture of complexing agent, and the oxidant is 5 10%Cl‑1+ 5 10%ClO‑1Aqueous solution, the complexing agent be it is a series of can be with Fe+2,3、Ni+2、Cr+2,3、Co+2,3Forming the aqueous solution of the inorganic anion water soluble compound of water soluble complex in aqueous solution Deng cation, the application method includes spray-on process, wipe method and infusion method, the advantage of the invention is that：It is moderate to etch decontamination speed, etching reaction speed, etch depth etc. are controllable, especially suitable for efficiently removing the radioactive pollutant of closed system inner surface, decontamination factor is very high, and the method for the invention decontamination process does not generate pollution environment and corrodes the NO of other equipment2And acid mist, explosive gas H is not generated2Etc. dangerous substances, decontamination process generate waste liquid dealt carefully with, do not generate the secondary waste that nuclear facilities waste disposal facilities cannot be handled.
Description
Technical field
The present invention relates to chemical field, in particular to a kind of metal surface radioactive pollution detergent and its users
Method.
Background technology
In nuclear facilities operational process, it is often necessary to carry out decontamination processing to the various metal parts by radioactive pollution；
In elimination of nuclear facilities field, frequently encounters the various glove boxes for operating radioactive substance, draught cupboard, operates radioactive substance
The dismounting of process pipe is retired, these equipment usually all have serious radioactive surface contamination, before dismounting, it is necessary to first decontamination
It removes, is on the hazard to avoid the radiation safety of staff and environment during disassembling operation is removed again.
Currently, the technology for being related to metal surface decontamination includes mainly：1. in contaminated surface brush peelable film, radiated after taking off film
Property substance remove surface radioactive pollution with film, this method is mainly used for the closing of surface radioactive substance, prevents retired process
In show that radioactive substance is arbitrarily spread, this method can only remove the loose contamination of contaminated surface, and it is shallow to be deep into basis material
The fixed-contamination object on surface layer cannot be removed thoroughly；2. using diluted " chloroazotic acid " or other detergent etching pollution tables containing HNO
Face, for example, Publication No. 200510134673.7 patented technology, use formula for HNO3-(NH4)2Ce(NO3)6Detergent go
Except metal surface radioactive pollution, but these two kinds of methods will produce a large amount of acid mists and NO2, pollution environment, corrosion facility in other
Useful equipment, and a large amount of radioactive decontamination waste liquids generated fail timely processing, the group 3. based on electrolysis electrochemical corrosion+ultrasound
Decontamination method is closed, the Patent Application Publication of this kind of technology includes：Publication No. CN101079334, CN101210343,
CN1080333, CN1986904, CN201220974, CN101714414A and CN101260527 etc., the common spy of these technologies
Point is complex technical process, will produce a certain amount of explosive gas hydrogen in decontamination process, this method cannot solve very well pipeline,
The decontamination problem of the inner surfaces such as container.
With the fast development of China's Nuclear Electricity, the operation and maintenance of nuclear facilities are badly in need of solving the fast decontaminating of Contaminated Parts
Problem, large quantities of old nuclear facilities exceed it and design service phase in succession, need to arrange for decontamination skill that is retired, therefore being related to inner surface pollution
Art has broad application prospects.
Invention content
The purpose of the present invention is to provide a kind of high-effective cleansing agent, it is especially useful in solves to put during radioactivity decommissioning
The decontamination of the inner surfaces such as radioactive pollution pipeline, large-scale Spent Radioactive liquid storage tank, glove box, draught cupboard.
In order to solve the above technical problems, technical solution provided by the invention is：A kind of metal surface radioactive pollution decontamination
Agent, the detergent are oxidant and the isometric mixture of complexing agent, and the oxidant is 5-10%Cl-1+ 5-10%ClO-1's
Aqueous solution, wherein Cl-1It is provided by soluble chloride, content is between 1-5w.t%, wherein ClO-1By water can be dissolved in
Hypochlorite provide, for content between 1-5w.t%, remaining is deionized water, the complexing agent be it is a series of can be with Fe+2,3、Ni+2、Cr+2,3、Co+2,3Form the inorganic anion water soluble compound of water soluble complex in aqueous solution Deng cation
Aqueous solution, for content between 5-10%, remaining is deionized water.
A kind of application method of metal surface radioactive pollution detergent, including spray-on process, wipe method and infusion method, described
Detergent is sprayed on surface to be decontaminated using the commercial nebulizer of resistance to strong acid, highly basic, stands 5-10 minutes, adopt by spray-on process
Exterior surface etch products, radioactive pollution substance are removed with wiping means, by the way that the above process is repeated several times；The wipe method,
The wiping head of hand-held acid and alkali-resistance after wiping head dips in detergent, then using wiping means goes exterior surface to pollute；The infusion method,
Using the liquid pump of resistance to strong acid, highly basic, detergent is pumped into the enclosure spaces such as pipeline to be decontaminated, storage tank, stands 5-10
After minute, detergent is discharged, repeated multiple times replacement detergent.
After the present invention uses above-mentioned technique, advantage is：Detergent etching decontamination speed of the present invention is moderate, etching
Reaction speed, etch depth etc. are controllable, especially suitable for efficiently removing the radioactive pollutant of closed system inner surface, decontamination because
Son is very high；The method of the invention decontamination process does not generate pollution environment and corrodes the NO of other equipment2And acid mist, it does not generate quick-fried
Fried property gas H2Etc. dangerous substances；The waste liquid that decontamination process generates is dealt carefully with, and does not generate nuclear facilities waste disposal facilities
The secondary waste that cannot be handled.
As an improvement, the soluble chloride is NaCl, the hypochlorite is NaClO and Ca (ClO)2。
As an improvement, the complexing agent is F-1, CN-, the ligands such as Ac-, after these substance single uses, or mixing
It uses.
Specific implementation mode
Illustrate the present invention with specific embodiment below, is not limitation of the present invention.
The spray-on process decontamination on 1 radioactive pollution surface of embodiment
Spraying device used in this decontamination method is market purchasing, which includes that be sealed and stored tank, detergent defeated for detergent
Hose, decontamination spray gun are sent, air compressor, by the oxidant of equal proportion, complexing agent detergent measuring tank injects detergent sealing
Hold-up tank starts air compressor to tank is sealed and stored and injects 0.09Mpa compressed airs, opens decontamination spray gun valve, will be in mist
The detergent that shape sprays is sprayed onto contaminated surface to be decontaminated, after standing 5-10 minutes, using wipe method removal surface etching production
Object can be used multilayer according to actual conditions and repeat decontamination.
Test result shows：(1) about 0.5 micron of the corrosion depth mean depth of 316 stainless steel substrate of the present embodiment pair；
(2) decontamination front surface level of pollution：8000Bq/cm2, after 3 decontaminations, contaminated surface level of pollution：1-4Bq/cm2, (3)
Generate solid radioactive wiping head 100g.
The etch effect of 2 detergent formulations pair of embodiment, 316 stainless steel is tested
It is injected separately into 50ml oxidants into 200ml beakers and complexing agent is uniformly mixed；Take correct amount, thickness be about
The 316 stainless steel band samples of 0.1mm；Leaching sample enters detergent；Observe etching reaction speed.
Detergent formulations one：Oxidant：5%Cl-1+ 5%ClO-1Aqueous solution；Complexing agent：5%Na F+5%KHC2O4It is water-soluble
Liquid, equal proportion mixing.
One test result of detergent formulations：Etching reaction is fast, temperature rise, and solution becomes blackish green, sample in 10 minutes
There is black oxide on surface corrosion, etching surface.
Detergent formulations two：Oxidant：2%Cl-1+ 2%ClO-1Aqueous solution；Complexing agent：2%Na F+2%KHC2O4It is water-soluble
Liquid, equal proportion mixing.
Two test result of detergent formulations：There is the gentle etching reaction of observable, solution becomes blackish green in 15 minutes, examination
There is black oxide on sample surface corrosion, etching surface.
The decontamination of 3 316 stainless steel planar surface radionuclide caesium of embodiment pollution
Decontamination step：By the oxidant of equal proportion, complexing agent detergent measuring tank injects detergent and is sealed and stored tank；Start
Air compressor injects 0.09Mpa compressed airs to tank is sealed and stored；Decontamination spray gun valve is opened, the decontamination that will be sprayed in mist
Agent is sprayed onto contaminated surface to be decontaminated, after standing 5-10 minutes；Surface etching product is removed using wipe method；According to practical feelings
Condition can be used multilayer and repeat decontamination；It is horizontal to detect gdna contamination radioactive surface contamination.
Test result shows：(1) the corrosion depth mean depth about 0.1-1.0 of 316 stainless steel substrate of the present embodiment pair is micro-
Rice；(2) hot spot surface level of pollution before decontamination：500Bq/cm2, decontamination rear surface level of pollution：0.5-1Bq/cm2。
The decontamination of 4 316 stainless steel uranium-bearing waste liquid conveyance conduit inner surface of embodiment pollution
Detergent conveying device used in this decontamination method is market purchasing, the device include detergent be sealed and stored tank,
Detergent delivery pump, conveyance conduit etc., by the oxidant of equal proportion, complexing agent detergent measuring tank injects detergent and is sealed and stored
Tank starts detergent delivery pump, opens conveyance conduit valve, detergent is transported to 316 stainless steel uranium-bearing waste liquid delivery pipes
In road, control pipeline valve makes detergent be sent into pipeline with certain speed from the pipeline other end, stands 30 minutes.
Test result shows：(1) the corrosion depth mean depth about 0.5-1.2 of 316 stainless steel substrate of the present embodiment pair is micro-
Rice；(2) hot spot surface level of pollution before decontamination：100Bq/cm2, decontamination rear surface level of pollution：0.2-0.5Bq/cm2。
The present invention is one kind not to environment row side (NO containing nitre2) exhaust gas, acid mist, do not generate explosion gas hydrogen safety it is high
Radioactive surface contamination's technology is imitated, is solved in other patents or the indeterminable closed pipe system of public technology, glove box
The depth decontamination problem of the radioactive pollution of wall, draught cupboard or container inner wall, low in the pollution of the environment, the radioactive wastewater that decontamination generates
It can be directly discharged into middle low level waste water processing system or the processing of cement solidification system of nuclear facilities with radioactivity mud, do not generate other
The secondary pollution that cannot be handled has novel, advanced feature.
Claims (4)
1. a kind of metal surface radioactive pollution detergent, it is characterised in that：The detergent is the bodies such as oxidant and complexing agent
Product mixture, the oxidant are 5-10%Cl-1+ 5-10%ClO-1Aqueous solution, wherein Cl-1It is provided by soluble chloride,
Its content is between 1-5w.t%, wherein ClO-1By can be dissolved in water hypochlorite provide, content between 1-5w.t%,
Remaining is deionized water, the complexing agent be it is a series of can be with Fe+2,3、Ni+2、Cr+2,3、Co+2,3In aqueous solution Deng cation
Formed water soluble complex inorganic anion water soluble compound aqueous solution, content between 5-10%, remaining for go from
Sub- water.
2. a kind of metal surface radioactive pollution detergent according to claim 1, it is characterised in that：The soluble chlorine
Compound is NaCl, and the hypochlorite is NaClO and Ca (ClO)2。
3. a kind of metal surface radioactive pollution detergent according to claim 1, it is characterised in that：The complexing agent is
F-1, CN-, the ligands such as Ac-, used after these substance single uses, or mixing.
4. a kind of application method of metal surface radioactive pollution detergent, including spray-on process, wipe method and infusion method, feature
It is：Detergent is sprayed on surface to be decontaminated using the commercial nebulizer of resistance to strong acid, highly basic, stands 5- by the spray-on process
10 minutes, exterior surface etch products, radioactive pollution substance are removed using wiping means, by the way that the above process is repeated several times；Institute
Wipe method is stated, the wiping head of acid and alkali-resistance is held, after wiping head dips in detergent, then goes exterior surface to pollute using wiping means；Institute
Infusion method is stated, using the liquid pump of resistance to strong acid, highly basic, detergent is pumped into the enclosure spaces such as pipeline to be decontaminated, storage tank,
After standing 5-10 minutes, detergent is discharged, repeated multiple times replacement detergent.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201810015754.2A CN108560003A (en) | 2018-01-08 | 2018-01-08 | A kind of metal surface radioactive pollution detergent and its application method |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201810015754.2A CN108560003A (en) | 2018-01-08 | 2018-01-08 | A kind of metal surface radioactive pollution detergent and its application method |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN108560003A true CN108560003A (en) | 2018-09-21 |
Family
ID=63530766
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201810015754.2A Pending CN108560003A (en) | 2018-01-08 | 2018-01-08 | A kind of metal surface radioactive pollution detergent and its application method |
Country Status (1)
| Country | Link |
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| CN (1) | CN108560003A (en) |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110047608A (en) * | 2019-05-20 | 2019-07-23 | 华核（天津）新技术开发有限公司 | Hand-held radiation contact scar decontamination method |
| CN111554427A (en) * | 2020-05-18 | 2020-08-18 | 中国核动力研究设计院 | Membrane stripping tool and process for removing dirt of strippable membrane in hot chamber |
| CN115641979A (en) * | 2022-10-26 | 2023-01-24 | 核工业北京化工冶金研究院 | Chemical method online decontamination device and decontamination method for pipeline |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110047608A (en) * | 2019-05-20 | 2019-07-23 | 华核（天津）新技术开发有限公司 | Hand-held radiation contact scar decontamination method |
| CN111554427A (en) * | 2020-05-18 | 2020-08-18 | 中国核动力研究设计院 | Membrane stripping tool and process for removing dirt of strippable membrane in hot chamber |
| CN111554427B (en) * | 2020-05-18 | 2022-02-11 | 中国核动力研究设计院 | Membrane stripping tool and process for removing dirt of strippable membrane in hot chamber |
| CN115641979A (en) * | 2022-10-26 | 2023-01-24 | 核工业北京化工冶金研究院 | Chemical method online decontamination device and decontamination method for pipeline |
| CN115641979B (en) * | 2022-10-26 | 2023-07-07 | 核工业北京化工冶金研究院 | Chemical method on-line decontamination device and decontamination method for pipeline |
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