CN101698941B - Technology for reducing fluorin residue on acid cleaned surface of zirconium alloy pipe - Google Patents
Technology for reducing fluorin residue on acid cleaned surface of zirconium alloy pipe Download PDFInfo
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- CN101698941B CN101698941B CN2009102185641A CN200910218564A CN101698941B CN 101698941 B CN101698941 B CN 101698941B CN 2009102185641 A CN2009102185641 A CN 2009102185641A CN 200910218564 A CN200910218564 A CN 200910218564A CN 101698941 B CN101698941 B CN 101698941B
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Abstract
The invention relates to the field of a technology for reducing fluorin residue on the acid cleaned surface of a zirconium alloy pipe, comprising the following steps: sequentially rinsing the zirconium alloy pipe with NH4CO3 solution and NaOH solution; rinsing the zirconium alloy pipe with hot softened water, and washing the zirconium alloy pipe with cold softened water; and blowing and scrubbing the zirconium alloy pipe by directly blowing with high-pressure gas or blowing and beating the surface of a sponge block to lead the surface of the zirconium alloy pipe to have no moisture and water print remnant to complete the process of reducing the fluorin residue on the acid cleaned surface of the zirconium alloy pipe. The invention can effectively reduce the fluorin residue which mainly is zirconium fluoride complex on the acid cleaned surface of the zirconium alloy pipe, improves the service life of the zirconium alloy pipe, sufficiently meet the use requirement of the zirconium alloy pipe in nuclear power, improves the manufacture technology of the zirconium alloy pipe in China, and enhances the use safety of nuclear materials.
Description
Technical field
The present invention relates to a kind of process field that reduces the zirconium alloy pipe fluorin residue on acid cleaned.
Background technology
Along with the development of nuclear power industry, people have proposed long-life, high burnup, zero damaged requirement to reactor fuel assemblies, to reduce the nuclear power production cost and to improve safety in operation, promote applying and popularizing of nuclear power.But improve the burnup of fuel element and prolong fuel cycle period fuel element is increased at in-pile time, the extent of corrosion of fuel canning material will aggravate with the prolongation at in-pile time.Therefore, the anti-water side corrosion of zirconium alloy cladding becomes the focus of problem.And most zirconium alloy tubes requirement product user modes are pickled surface, and pickling is carried out in the mix acid liquor of industrial hydrofluoric acid, industrial nitric acid and water, and complicated chemical reaction takes place in this mix acid liquor the zirconium material.Data shows that zirconium alloy tube will deposit fluorine residues such as forming the zirconium fluoride complex compound inevitably in the transfer process of pickling, washing on the zirconium alloy pipe surfaces externally and internally.If can not reduce effectively on the zirconium alloy pipe pickled surface with the zirconium fluoride complex compound is master's fluorine residue; Will quicken the corrosion of zircaloy; Cause the material property of zirconium alloy tube sharply to worsen, significantly shorten the service life of zirconium alloy tube and can in use cause very serious security incident.But how to reduce the zirconium fluoride complex compound at present effectively is that main fluorine residue is an important topic of being badly in need of solution during nuclear-used zirconium alloy tubing is produced.The process research that at present abroad reduces fluorine residue for zircaloy surface, zircaloy surface also is in the stage of fumbling, and domestic research for does not in this respect almost have.
Summary of the invention
It is to be solved by this invention that to provide a kind of can effectively the reduction on the zirconium alloy pipe pickled surface with the zirconium fluoride complex compound be the method for master's fluorine residue; Improve the decay resistance and the service life of zirconium alloy pipe; Produce and to satisfy the zirconium alloy pipe of nuclear power with material and demand for security; Improve China's zirconium alloy pipe production technology level, assurance nuclear is safe in utilization with material.
The present invention is for solving the problems of the technologies described above, and the technical scheme of employing is:
The concrete steps that reduce the process implementation process of zirconium alloy pipe fluorin residue on acid cleaned are:
A) use NH
4HCO
3Solution embathes, and the zirconium alloy pipe after the pickling is put into NH
4HCO
3Embathe in the solution, the time of embathing is 60～90 seconds;
Wherein, NH
4HCO
3Each component volume ratio of solution is: NH
4HCO
3: demineralized water=1: 10;
Wherein zirconium alloy pipe is put into NH
4HCO
3Embathe in the solution, be meant to let zirconium alloy pipe at the uniform velocity immerse NH with certain gradient along its length direction
4HCO
3Do upper and lower swing after in the solution;
B) embathe with NaOH solution, will use NH
4HCO
3Zirconium alloy pipe after solution embathes is put into prepared NaOH solution and is embathed, and embathing temperature is 45 ℃～55 ℃, and the time of embathing is 60～90 seconds;
Wherein said prepared NaOH solution; Be meant through at first demineralized water being put into container; According to NaOH: the volume ratio of demineralized water=1: 10 adds corresponding N aOH, then above container, comes and goes stirring at least 5 times, the NaOH solution of processing after stirring with sticking plaster;
Each component volume ratio of wherein said prepared NaOH solution is: NaOH: demineralized water=1: 10;
Wherein saidly will use NH
4H CO
3Should be controlled at 5 to 10 seconds the transfer time that zirconium alloy pipe after solution embathes is put into prepared NaOH solution;
Wherein said zirconium alloy pipe is put into prepared NaOH solution and is embathed, and is meant to let zirconium alloy pipe after its length direction at the uniform velocity immerses in the prepared NaOH solution with certain gradient, do upper and lower swing;
C) the thermal softening water logging is washed, and zirconium alloy pipe is put into demineralized water embathe, and the time of embathing is 60～90 seconds, and wherein the temperature of demineralized water is 70 ℃～80 ℃;
Wherein said zirconium alloy pipe is put into demineralized water and is embathed, and is meant to let zirconium alloy pipe after its length direction at the uniform velocity immerses in the demineralized water with certain gradient, do upper and lower swing;
D) cold demineralized water flushing is washed zirconium alloy pipe with demineralized water, and washing time is 80～90 seconds, and wherein the temperature of demineralized water is 15 ℃～20 ℃;
Wherein saidly wash zirconium alloy pipe with demineralized water; Be meant that zirconium alloy pipe is inserted demineralized water to be embathed after 20 seconds and take out; At the uniform velocity wash the inner surface and the outer surface of zirconium alloy pipe immediately with demineralized water, the time of flushing zirconium alloy pipe inner surface and outer surface must not be less than 30 seconds respectively;
E) blow wiping, after demineralized water flushing, directly blow with the gases at high pressure of cleaning immediately or sponge block piping and druming inner surface residual until no moisture and water mark;
The pH value of the demineralized water that is wherein adopted is 6～7, and hardness is not more than 0.6me/L;
The invention has the beneficial effects as follows; Adopting this method invention to effectively reduce on the zirconium alloy pipe pickled surface with the zirconium fluoride complex compound is master's fluorine residue; Improve the service life of zirconium alloy pipe; Fully satisfied the instructions for use of nuclear power, improved China's zirconium alloy pipe production technology level, increased the safety in utilization of nuclear with material to zirconium alloy pipe.
The specific embodiment
Do a detailed description below in conjunction with the practical implementation process that reduces fluorine residue on the nuclear-used zirconium alloy pipe pickled surface that specification is Ф 13 * 1mm, the practical implementation step is:
A) use NH
4HCO
3Solution embathes, and the angle that the Ф 13 * 1mm zirconium alloy pipe after the pickling is spent with its length direction and horizontal plane about 45 at the uniform velocity immerses NH
4HCO
3Do upper and lower swing after in the solution, the time of embathing is 75 seconds, wherein NH
4HCO
3Each component volume ratio is in the solution: NH
4HCO
3: demineralized water=1: 10;
B) embathe with NaOH solution, will use NH
4HCO
3After at the uniform velocity immersing in the prepared NaOH solution, the angle that the zirconium alloy pipe of Ф 13 * 1mm after solution embathes is spent with its length direction and horizontal plane about 45 does upper and lower swing; Embathing temperature is about 45 ℃～55 ℃; The time of embathing is about 75 seconds, and wherein each component volume ratio of prepared NaOH solution is: NaOH: demineralized water=1: 10;
Wherein prepared NaOH solution is meant through at first demineralized water being put into container; According to NaOH: the volume ratio of demineralized water=1: 10 adds corresponding N aOH; Then above container, come and go and stir at least 5 times with sticking plaster; The NaOH solution of processing after stirring is heated to 45 ℃～55 ℃ and insulation with prepared NaOH solution subsequently;
Wherein will use NH
4HCO
3Ф 13 * 1mm zirconium alloy pipe after solution embathes at the uniform velocity takes out puts into prepared NaOH solution, and the whole time was controlled in 5 to 10 seconds;
C) the thermal softening water logging is washed, with Ф 13 * 1mm zirconium alloy pipe do upper and lower swing after at the uniform velocity immersing in the demineralized water with the angle of about 45 degree of its length direction and horizontal plane; Put into demineralized water and embathe, the time of embathing is 60～90s, and wherein the temperature of demineralized water is 70 ℃～80 ℃;
Wherein to be 70 ℃～80 ℃ be to stop heating about 70 ℃～80 ℃ and insulation back obtains through demineralized water being put into another container, heating rod is put into demineralized water, being heated to the temperature of demineralized water;
D) cold demineralized water flushing is washed zirconium alloy pipe with demineralized water, and washing time is 60～90s, and the temperature of demineralized water is 15 ℃～20 ℃;
Wherein be meant that with demineralized water flushing zirconium alloy pipe zirconium alloy pipe is inserted demineralized water to be embathed and take out after 20 seconds, at the uniform velocity wash the inner surface and the outer surface of zirconium alloy pipe immediately with demineralized water, the time of flushing zirconium alloy pipe inner surface and outer surface must not be less than 30 seconds respectively;
F) blow wiping, after demineralized water flushing, directly blow with the gases at high pressure of cleaning immediately or sponge block piping and druming inner surface residual until no moisture and water mark; In blowing the process of drying, operating personnel need wear clean white gloves;
Wherein, the pH value of demineralized water is 6～7, and hardness is not more than 0.6me/L;
Be to carry out the fluorine ion residue detection after the pickled surface of the zirconium alloy pipe of Ф 13 * 1mm reduces fluorine residue to specification.Testing result is following:
After adopting this method invention, the fluorine residue of zirconium alloy pipe pickled surface can reduce by 45%～55%.
Claims (2)
1. a process that reduces the zirconium alloy pipe fluorin residue on acid cleaned is characterized in that, the concrete process that reduces the zirconium alloy pipe fluorin residue on acid cleaned follows these steps to carry out:
A) use NH
4HCO
3Solution embathes: the zirconium alloy pipe after the pickling is put into NH
4HCO
3Embathe in the solution, the time of embathing is 60～90 seconds, wherein NH
4HCO
3Each component volume ratio of solution is: NH
4HCO
3: demineralized water=1: 10, wherein the zirconium alloy pipe after the pickling is put into NH
4HCO
3Embathe in the solution and be meant and let zirconium alloy pipe at the uniform velocity immerse NH with certain gradient along its length direction
4HCO
3Do upper and lower swing after in the solution;
B) embathe with NaOH solution: will use NH
4HCO
3Zirconium alloy pipe after solution embathes is put into prepared NaOH solution and is embathed, and embathing temperature is 45 ℃～55 ℃, and the time of embathing is 60～90 seconds, wherein will use NH
4HCO
3Should be controlled at 5 to 10 seconds the transfer time that zirconium alloy pipe after solution embathes is put into prepared NaOH solution, and wherein each component volume ratio of prepared NaOH solution is: NaOH: demineralized water=1: 10; Wherein zirconium alloy pipe being put into prepared NaOH solution embathes and is meant and lets zirconium alloy pipe along its length direction at the uniform velocity immerses prepared NaOH solution with certain gradient after, do upper and lower swing;
C) the thermal softening water logging is washed: zirconium alloy pipe is put into demineralized water embathe; The time of embathing is 60～90 seconds; Wherein the temperature of demineralized water is 70 ℃～80 ℃, and wherein zirconium alloy pipe is put into demineralized water and embathed and be meant and let zirconium alloy pipe along its length direction at the uniform velocity immerses demineralized water with certain gradient after, do upper and lower swing;
D) cold demineralized water flushing: wash zirconium alloy pipe with demineralized water; Washing time is 90 seconds; Wherein the temperature of demineralized water is 15 ℃～20 ℃; Wherein demineralized water flushing zirconium alloy pipe is meant that zirconium alloy pipe is inserted demineralized water to be embathed and take out after 20 seconds, at the uniform velocity washes the inner surface and the outer surface of zirconium alloy pipe immediately with demineralized water, and the time of flushing zirconium alloy pipe inner surface and outer surface must not be less than 30 seconds respectively;
E) blow wiping: after demineralized water flushing, directly blow with the gases at high pressure of cleaning immediately or sponge block piping and druming inner surface residual until no moisture and water mark;
The pH value of the demineralized water that is wherein adopted is 6～7, and hardness is not more than 0.6me/L.
2. according to the process of the said reduction zirconium alloy pipe of claim 1 fluorin residue on acid cleaned; It is characterized in that; The described prepared NaOH solution of step b) is meant through at first demineralized water being put into container; According to NaOH: the volume ratio of demineralized water=1: 10 adds corresponding N aOH, then above container, comes and goes stirring at least 5 times, the NaOH solution of processing after stirring with sticking plaster.
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|---|---|---|---|
| CN2009102185641A CN101698941B (en) | 2009-10-29 | 2009-10-29 | Technology for reducing fluorin residue on acid cleaned surface of zirconium alloy pipe |
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|---|---|---|---|
| CN2009102185641A CN101698941B (en) | 2009-10-29 | 2009-10-29 | Technology for reducing fluorin residue on acid cleaned surface of zirconium alloy pipe |
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| CN101698941B true CN101698941B (en) | 2012-03-21 |
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Families Citing this family (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104911660A (en) * | 2015-05-25 | 2015-09-16 | 常熟锐钛金属制品有限公司 | Treatment process for long service life zirconium pipe |
| CN107640745B (en) * | 2017-09-19 | 2020-01-17 | 中国核动力研究设计院 | Method for extracting residual fluorine on inner surface of zirconium alloy pipe |
| CN111364046B (en) * | 2020-03-16 | 2023-10-31 | 宁夏中色金航钛业有限公司 | Brightening pickling method for rare metal and alloy processing material thereof and pickling solution |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101380636A (en) * | 2007-08-27 | 2009-03-11 | 应用材料公司 | Wet clean process for recovery of anodized chamber parts |
| CN101497074A (en) * | 2008-01-29 | 2009-08-05 | 中芯国际集成电路制造(上海)有限公司 | Method for removing fluorine residue in manufacture process of semi-conductor |
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Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101380636A (en) * | 2007-08-27 | 2009-03-11 | 应用材料公司 | Wet clean process for recovery of anodized chamber parts |
| CN101497074A (en) * | 2008-01-29 | 2009-08-05 | 中芯国际集成电路制造(上海)有限公司 | Method for removing fluorine residue in manufacture process of semi-conductor |
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Owner name: STATE NUCLEAR BAO TI ZIRCONIUM INDUSTRY COMPANY Free format text: FORMER OWNER: NORTHWEST ZIRCOCLADDING CO., LTD. Effective date: 20120704 Owner name: NORTHWEST ZIRCOCLADDING CO., LTD. Effective date: 20120704 |
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Free format text: CORRECT: ADDRESS; FROM: 721014 DISTRICT 2, NO.1, TAICHENG ROAD, WEIBIN DISTRICT, BAOJI CITY, SHANXIPROVINCE TO: 721014 NO.206, BAOJI CITY HIGH AVENUE, SHANXI PROVINCE |
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Effective date of registration: 20120704 Address after: 721014 No. 206, hi tech Avenue, Shaanxi, Baoji Co-patentee after: Northwest Zircocladding Co., Ltd. Patentee after: State Nuclear Bao Ti Zirconium Industry Company Address before: 721014, No. 2, block 1, Ti Cheng Road, Weibin District, Shaanxi, Baoji Patentee before: Northwest Zircocladding Co., Ltd. |