氨水溶液在γ场中的稳态辐射分解行为研究

郭子方; 杨雨; 林铭章; 曹骐; 汤嘉; 林蕴良; 林子健

doi:10.13832/j.jnpe.2023.03.0217

氨水溶液在γ场中的稳态辐射分解行为研究

doi: 10.13832/j.jnpe.2023.03.0217

郭子方^1,,
杨雨^{1, 2},
林铭章^1, ,,
曹骐²,
汤嘉²,
林蕴良¹,
林子健¹

1.
中国科学技术大学核科学技术学院，合肥，230026
2.
中国核动力研究设计院，成都，610213

基金项目: 国家自然科学基金（11775214）

详细信息

作者简介:
郭子方（1995—），男，博士研究生，现主要从事水溶液辐射化学研究，E-mail: gzf1212@mail.ustc.edu.cn

通讯作者:
林铭章，E-mail: gelin@ustc.edu.cn

中图分类号: TL99；O644
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- 被引次数: 0
出版历程
- 收稿日期: 2022-07-01
- 修回日期: 2022-07-13
- 刊出日期: 2023-06-15

Study on the Steady γ-Radiolysis of Ammonia Solution

Guo Zifang^1
,,
Yang Yu^{1, 2},
Lin Mingzhang^{1
, ,},
Cao Qi²,
Tang Jia²,
Lin Yunliang¹,
Lin Zijian¹

1.
School of Nuclear Science and Technology, University of Science and Technology of China, Hefei, 230026, China
2.
Nuclear Power Institute of China, Chengdu, 610213, China

摘要

摘要: 含氨冷却剂被应用于压水堆中，可以清除冷却剂辐射分解产生的O₂、H₂O₂等氧化性产物，从而减轻结构材料腐蚀。本文研究了氨水在γ辐射场中的辐射分解行为，考察氨浓度、辐射吸收剂量和吸收剂量率、气液体积比和不同饱和气体对氨水辐射分解行为的影响，重点关注辐射分解产物H₂O₂和NO₂⁻的浓度变化。结果表明，随着体系中氨浓度的增加，H₂O₂的浓度受到明显抑制，NO₂⁻的浓度则呈现出上升趋势；吸收剂量的增加使得H₂O₂浓度明显升高，NO₂⁻的浓度则在吸收剂量为8 kGy时达到最大（> 100 μmol/L），而后降低；吸收剂量率的差异（2.78~25 Gy/min）并未导致H₂O₂和NO₂⁻浓度产生明显变化；氨水中的O₂是NO₂⁻生成的关键，但O₂过多会促进NO₂⁻氧化为NO₃⁻从而降低NO₂⁻浓度，此外O₂的存在促进了H₂O₂的生成。本文研究结果可为后续含氨冷却剂体系的优化提供参考。
- 氨 /
- 冷却剂 /
- 辐射分解 /
- 反应堆 /
- 水化学
Abstract: Ammonia is applied in the coolant to eliminate the O₂ and H₂O₂ in the PWR, thus mitigating the corrosion of structural materials. The present work studied the γ-radiolysis of ammonia solution under different conditions including ammonia concentration, absorbed dose, absorbed dose rate, gas-liquid volume ratio, and different saturated gases. The results show that ammonia significantly inhibits H₂O₂ because of the consumption of H₂O₂ and suppression of its precursors. The concentration of NO₂⁻ rises with the ammonia concentration . Ammonia is continuously consumed as irradiation progresses, while the concentration of H₂O₂ increases significantly with the absorbed dose. The NO₂⁻ reaches a peak maximum (> 100 μmol/L) when the absorbed dose is 8 kGy. However, NO₂⁻ has a drop when the absorbed dose grows further, due to the fact O₂ oxidizes NO₂⁻ into NO₃⁻. The concentrations of H₂O₂ and NO₂⁻ are not obviously affected within the absorbed dose rate range (2.78~25 Gy/min). The presence of O₂ is critical to the formation of NO₂⁻, though excessive O₂ in the system could lead to the oxidization of NO₂⁻ by increasing the oxidizing species. Besides, the oxygen dissolved in aqueous ammonia promotes the production of H₂O₂. This work is expected to provide a helpful reference for the optimization of the ammonia-containing coolant system.
- Ammonia /
- Coolant /
- Radiolysis /
- Reactor /
- Water chemistry

HTML全文

图 1 氨浓度对H₂O₂和NO₂⁻浓度的影响

Figure 1. Concentrations of H₂O₂ and NO₂⁻ under Different Ammonia Concentrations

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图 2 吸收剂量对H₂O₂和NO₂⁻浓度的影响

Figure 2. Concentrations of H₂O₂ and NO₂⁻ under Different Absorbed Doses

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图 3 吸收剂量率对H₂O₂和NO₂⁻浓度的影响

Figure 3. Concentrations of H₂O₂ and NO₂⁻ under Different Absorbed Dose Rates

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图 4 气液体积比对H₂O₂和NO₂⁻浓度的影响

Figure 4. Concentrations of H₂O₂ and NO₂⁻ under Different Gas-liquid Volume Ratios

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图 5 不同饱和气体对H₂O₂和NO₂⁻浓度的影响

Figure 5. Concentrations of H₂O₂ and NO₂⁻ under Different Saturated Gases

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参考文献(19)

[1]	WREN J C. Steady-state radiolysis: effects of dissolved additives[M]. United States: ACS Publications, 2010: 271-295.
[2]	UCHIDA S, KATSUMURA Y. Water chemistry technology – one of the key technologies for safe and reliable nuclear power plant operation[J]. Journal of Nuclear Science and Technology, 2013, 50(4): 346-362. doi: 10.1080/00223131.2013.773171
[3]	ELLIOT A, BARTELS D. The reaction set, rate constants and g-values for the simulation of the radiolysis of light water over the range 20℃ to 350℃ based on information available in 2008: AECL-153-127160-450-001[R]. Canada: Atomic Energy of Canada Limited, 2009
[4]	DAUB K, ZHANG X, NOËL J J, et al. Effects of γ-radiation versus H₂O₂ on carbon steel corrosion[J]. Electrochimica Acta, 2010, 55(8): 2767-2776. doi: 10.1016/j.electacta.2009.12.028
[5]	BULANOV A V, KOLESOV B I, LUKASHENKO M L, et al. Radiolysis of ammonia in the first-loop coolant of reactors in floating power-generating units[J]. Atomic Energy, 2000, 88(5): 368-372. doi: 10.1007/BF02680531
[6]	HICKEL B, SEHESTED K. Reaction of hydroxyl radicals with ammonia in liquid water at elevated temperatures[J]. International Journal of Radiation Applications and Instrumentation. Part C. Radiation Physics and Chemistry, 1992, 39(4): 355-357. doi: 10.1016/1359-0197(92)90244-A
[7]	PAGSBERG P B. Investigation of the NH2 radical produced by pulse radiolysis of ammonia in aqueous solution: RISØ-256[R]. Denmark: Danish Atomic Energy Commission, 1972.
[8]	NETA P, MARUTHAMUTHU P, CARTON P M, et al. Formation and reactivity of the amino radical[J]. The Journal of Physical Chemistry, 1978, 82(17): 1875-1878. doi: 10.1021/j100506a004
[9]	LUZAKOV A V, BULANOV A V, VERKHOVSKAYA A O, et al. Radiation-chemical removal of corrosion hydrogen from VVER first-loop coolant[J]. Atomic Energy, 2008, 105(6): 402-407. doi: 10.1007/s10512-009-9115-4
[10]	RIGG T, SCHOLES G, WEISS J. 580. Chemical actions of ionising radiations in solutions. Part X. The action of X-rays on ammonia in aqueous solution[J]. Journal of the Chemical Society (Resumed), 1952: 3034-3038.
[11]	DWIBEDY P, KISHORE K, DEY G R, et al. Nitrite formation in the radiolysis of aerated aqueous solutions of ammonia[J]. Radiation Physics and Chemistry, 1996, 48(6): 743-747. doi: 10.1016/S0969-806X(96)00037-0
[12]	GHORMLEY J A. Warming curves for the condensed product of dissociated water vapor and for hydrogen peroxide glass[J]. Journal of the American Chemical Society, 1957, 79(8): 1862-1865. doi: 10.1021/ja01565a025
[13]	SHINN M B. Colorimetric method for determination of nitrate[J]. Industrial & Engineering Chemistry Analytical Edition, 1941, 13(1): 33-35.
[14]	LIU Z, FANG Z, WANG L, et al. Alpha radiolysis of nitric acid aqueous solution irradiated by ²³⁸Pu source[J]. Nuclear Science and Techniques, 2017, 28(4): 54. doi: 10.1007/s41365-017-0200-4
[15]	BUXTON G V, GREENSTOCK C L, HELMAN W P, et al. Critical Review of rate constants for reactions of hydrated electrons, hydrogen atoms and hydroxyl radicals (·OH/·O⁻) in Aqueous Solution[J]. Journal of Physical and Chemical Reference Data, 1988, 17(2): 513-886. doi: 10.1063/1.555805
[16]	彭静, 郝燕, 魏根栓, 等. 辐射化学基础教程[M]. 北京: 北京大学出版社, 2015: 186-187.
[17]	STEINBERG M. Irradiation of NH₃-H₂O solutions for formation of hydrazine: BNL-613(T-183)[R]. United States: Brookhaven National Laboratory, 1960
[18]	BUXTON G V, DAINTON F S. Radical and molecular yields in the γ-radiolysis of water. II. The potassium iodide-nitrous oxide system in the pH range 0 to 14[J]. Proceedings of the Royal Society of London. Series A. Mathematical and Physical Sciences, 1965, 287(1411): 427-443.
[19]	SCHULER R H, PATTERSON L K, JANATA E. Yield for the scavenging of hydroxyl radicals in the radiolysis of nitrous oxide-saturated aqueous solutions[J]. Journal of Physical Chemistry, 1980, 84(16): 2088-2089. doi: 10.1021/j100453a020