核石墨与水蒸气氧化腐蚀特性研究

申腾; 王城喻; 郭少强; 贺楷

doi:10.13832/j.jnpe.2024.090008

核石墨与水蒸气氧化腐蚀特性研究

doi: 10.13832/j.jnpe.2024.090008

申腾^1,,
王城喻^{2, 3},
郭少强^2, ,,
贺楷¹

1.
中国核电工程有限公司，北京，100840
2.
西安交通大学核科学与核技术学院，西安，710049
3.
上海交通大学机械与动力工程学院，上海，200240

详细信息

作者简介:
申　腾（1988—），男，硕士研究生，现主要从事耐高温慢化材料方面的研究，E-mail: shenteng@cnpe.cc

通讯作者:
郭少强，E-mail: guos2019@mail.xjtu.edu.cn

中图分类号: TL342
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- 被引次数: 0
出版历程
- 收稿日期: 2024-09-09
- 修回日期: 2024-11-04
- 刊出日期: 2025-08-15

Study on Oxidation Corrosion of Nuclear Graphite by Water Vapor

Shen Teng^1
,,
Wang Chengyu^{2, 3},
Guo Shaoqiang^{2
, ,},
He Kai¹

1.
China Nuclear Power Engineering Co., Ltd., Beijing, 100840, China
2.
School of Nuclear Science and Technology, Xi’an Jiaotong University, Xi’an, 710049, China
3.
School of Mechanical Engineering, Shanghai Jiaotong University, Shanghai, 200240, China

摘要

摘要: 为研究核石墨与水蒸气的氧化腐蚀反应特性，建立基于经典Langmuir-Hinshelwood（L-H）模型的石墨-水蒸气氧化腐蚀反应模型，开展了基于气体浓度法的石墨与水蒸气氧化腐蚀实验。实验结果显示在氦气水蒸气的混合气体流量为10 L/min且水蒸气浓度为3%~10%的实验工况下，温度大于950℃或1000℃时有气体产物CO₂生成，另外在混合气体中添加1%H₂未发现对氧化腐蚀速率有显著影响，这些与经典L-H模型有明显区别。因此，基于本研究的实验结果，提出了新的反应模型，增加了石墨与水蒸气反应生成CO₂和H₂的反应，去掉了L-H模型氢分压项，并使用实验数据完成了新模型的建模及验证。研究结果显示，新模型适用于水蒸气浓度相对高时的石墨-水蒸气氧化腐蚀模拟，能够相对准确地分析计算氧化腐蚀速率和气体生成速率。
- 核石墨 /
- 水蒸气 /
- 活化能 /
- 氧化腐蚀 /
- 反应模型
Abstract: In order to study the oxidation reaction properties of nuclear graphite by water vapor and establish the graphite-water vapor corrosion reaction model based on classical Langmuir-Hinshelwood (L-H) model, we conducted the experiments on the oxidation corrosion of graphite by water vapor based on gas concentration method. The experiment results demonstrated that CO₂ was generated at the temperature higher than 950℃ or 1000℃ in the experimental condition of the helium and water vapor mixed gas flow rate of 10 L/min and the water vapo concentration of 3% to 10%, and the mixture added with 1% H₂ has no obviously influence on reaction rate, which had obviously difference with classical L-H model. As a result, new reaction model was established based on the experiment results, which added the oxidation reaction of graphite by water vapor generating CO₂ and H₂ and removed the H₂ partial pressure term in L-H model. The experiment data was used to build a new model and verify the model respectively. The study results demonstrated that the new model was suitable for the simulation of oxidation of graphite by water vapor at a relative high water vapor concentration, which could relatively accurately analyze and calculate the corrosion rate and gas generating rate.
- Nuclear graphite /
- Water vapor /
- Activation energy /
- Oxidation corrosion /
- Reaction mechanism

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图 1 石墨腐蚀实验台架工作原理图

Figure 1. Schematic Diagram of Graphite Corrosion Experiment Bench

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图 2 气体产物归一化浓度与腐蚀实验温度的关系

Figure 2. Relationship between the Normalized Concentration of Gas Products and Corrosion Experiment Temperature

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图 3 实验中石墨-水蒸气腐蚀速率与温度关系

阴影区—R1数据拟合区；lnR_$f_{{\mathrm{H}}_2{\mathrm{O}}} $=a%—水蒸气浓度a%的实验条件下的总反应速率R的对数；lnR_bx_$f_{{\mathrm{H}}_2{\mathrm{O}}} $=a%—水蒸气浓度a%的实验条件下反应速率R_bx（x=1,2）的对数。

Figure 3. Relationship between the Corrosion Rate of Graphite by Water Vapor and the Temperature in the Experiment

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图 4 R1反应腐蚀速率实验值与拟合结果

$f_{{\mathrm{H}}_2{\mathrm{O}}} $—水蒸气的浓度；EXP—试验数据点；FIT—拟合曲线。

Figure 4. Corrosion Rate of R1 Reaction in Experiment and Fitting Result

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图 5 R2反应腐蚀速率实验值与拟合结果

Figure 5. Corrosion Rate of R2 Reaction in Experiment and Fitting Result

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图 6 水蒸气的反应级数

Figure 6. Reaction Order for Water Vapor

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图 7 实验与计算的腐蚀速率对比

Figure 7. Comparison between Experimental and Calculated Corrosion Rates

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图 8 实验与计算的CO浓度对比

Figure 8. Comparison between Experimental and Calculated CO Concentrations

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图 9 实验与计算的CO₂浓度对比

Figure 9. Comparison between Experimental and Calculated CO₂ Concentrations

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图 10 实验与计算的失重率对比

Figure 10. Comparison between Experimental and Calculated Weight Lose Rates

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表 1 国产核级石墨和IG110的物理性质对比

Table 1. Physical Property Comparasion of Domestic Nuclear Graphite and IG110

石墨类型	密度 / (g·cm⁻³)	孔隙率/%	热膨胀系数/10⁻⁶K^–1	杨氏模量/ GPa	抗压强度/ MPa	杂质含量/ (μg·kg⁻¹)
国产核级石墨	1.83	12	4.8	11	77	≤10
IG110	1.76	19	4.5	9	71	13

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表 2 核石墨与水蒸气腐蚀实验工况

Table 2. Experimental Conditions for Corrosion of Nuclear Graphite by Water Vapor

实验编号	温度/℃	总进气流量/(L·min⁻¹)	H₂O浓度/%	H₂浓度/%	实验编号	温度/℃	总进气流量/(L·min⁻¹)	H₂O浓度/%	H₂浓度/%
2101	800	10	5	0	2201	800	10	5	1
2103	900	10	5	0	2202	900	10	5	1
2105	950	10	5	0	2203	1000	10	5	1
2107	1000	10	5	0	2204	1100	10	10	1
2109	1100	10	5	0	2301	800	10	3	0
2102	800	10	10	0	2302	900	10	3	0
2104	900	10	10	0	2303	1000	10	3	0
2106	950	10	10	0	2304	1100	10	3	0
2108	1000	10	10	0	2401	800	5	5	0
2110	1100	10	10	0	2402	1000	5	5	0
					2403	800	20	5	0
					2404	1000	20	5	0

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表 3 腐蚀模型动力学参数

Table 3. Kinetic Parameter of Corrosion Model

数据来源	反应	参数值
拟合结果	R1	A₁=15.3836 Pa^–m·s⁻¹，A₃ =0.5128 Pa^–m，E_a1=174.39 kJ·mol⁻¹，E_a3=61.01 kJ·mol⁻¹
拟合结果	R2	A₄=7.6×10⁴ Pa⁻¹·s⁻¹，E_a4=363.2 kJ·mol⁻¹
Contescu^[2]	R1	A_1,0=900 Pa^–m·s⁻¹，A_2,0=110 Pa^−0.5，A_3,0=30 Pa^−m，E_a1,0=274 kJ·mol⁻¹，E_a2,0=74.66 kJ·mol⁻¹， E_a3,0=95.85 kJ·mol⁻¹，m_max =1.50，T₀ =1.33×10³K， $ \theta $=34.2 K

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