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 PDF

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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
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CN
China
Prior art keywords
detergent
decontamination
aqueous solution
metal surface
radioactive pollution
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CN201810015754.2A
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Chinese (zh)
Inventor
贾娅奇
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Mianyang Ke Da Chang Chuang Technology Co Ltd
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Mianyang Ke Da Chang Chuang Technology Co Ltd
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Priority to CN201810015754.2A priority Critical patent/CN108560003A/en
Publication of CN108560003A publication Critical patent/CN108560003A/en
Pending legal-status Critical Current

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    • CCHEMISTRY; METALLURGY
    • C23COATING 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
    • C23GCLEANING OR DE-GREASING OF METALLIC MATERIAL BY CHEMICAL METHODS OTHER THAN ELECTROLYSIS
    • C23G1/00Cleaning or pickling metallic material with solutions or molten salts
    • C23G1/02Cleaning or pickling metallic material with solutions or molten salts with acid solutions

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  • 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

A kind of metal surface radioactive pollution detergent and its application method
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.
CN201810015754.2A 2018-01-08 2018-01-08 A kind of metal surface radioactive pollution detergent and its application method Pending CN108560003A (en)

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Cited By (3)

* Cited by examiner, † Cited by third party
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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Cited By (5)

* Cited by examiner, † Cited by third party
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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