基于四步反应模型的石墨氧化腐蚀研究

申腾; 王城喻; 郭少强; 贺楷

doi:10.13832/j.jnpe.2025.01.0169

基于四步反应模型的石墨氧化腐蚀研究

doi: 10.13832/j.jnpe.2025.01.0169

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，北京，100084
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剂方面的研究，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
计量
- 文章访问数: 125
- HTML全文浏览量: 73
- PDF下载量: 6
- 被引次数: 0
出版历程
- 收稿日期: 2024-05-09
- 修回日期: 2024-07-04
- 刊出日期: 2025-02-15

Investigation of Graphite Oxidation Based on Four-step Reaction Model

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

1.
China Nuclear Power Engineering Co., Ltd., Beijing, 100084, China
2.
School of Nuclear Science and Technology, Xi’an Jiaotong University, Xi’an, 710049, China
3.
School of Mechanical Engineering, Shanghai Jiao Tong University, Shanghai, 200240, China

摘要

摘要: 为了建立气冷微堆堆芯石墨与氧气的腐蚀反应分析方法，本文基于Arrhenius反应式建立石墨氧化腐蚀的四步反应模型。模型的四步反应分别代表石墨与氧气在反应过程中可能发生的4种化学反应，并增加了反应活性面积以模拟失重率对腐蚀速率的影响。通过开展基于气体浓度法的石墨氧化腐蚀实验，得到500~1100℃下不同流量和不同氧气浓度的石墨氧化腐蚀速率，实验数据分别用于腐蚀参数拟合和模型验证。建模及验证分析结果表明，所拟合的四步反应模型能够适用于石墨氧化腐蚀速率的计算分析并能够区分反应产物，且模型反应活性面积的增加更有利于准确预测高失重下的氧化腐蚀速率。
- 石墨 /
- 氧化 /
- 活化能 /
- 实验 /
- 反应模型
Abstract: In order to establish the analysis method of corrosion reaction between graphite and oxygen in the core of Micro Gas-Cooled Reactor, a four-step reaction model of graphite oxidation corrosion is established based on Arrhenius equation. The four-step reaction of the model represents four possible chemical reactions between graphite and oxygen, and the reactive area is increased to simulate the influence of weight loss rate on corrosion rate. Through the experiment of graphite oxidation corrosion based on gas concentration method, the oxidation corrosion rates of graphite with different gas flow rates and oxygen concentrations at 500-1100°C were obtained, and the experimental data were used for corrosion parameter fitting and model verification respectively. The results of modeling and verification analysis show that the fitted four-step reaction model can be applied to the calculation and analysis of the oxidation corrosion rate of graphite and can distinguish the reaction products, and the increase of the reactive area of the model is more conducive to accurately predicting the oxidation corrosion rate under high weight loss.
- Graphite /
- Oxidation /
- Activation energy /
- Experiment /
- Reaction model

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图 1 石墨氧化腐蚀实验台架示意图

Figure 1. Sketch Map of Graphite Oxidation Experiment Bench

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图 2 10 L/min（标准工况下）流量和不同O₂浓度下的r与T关系

Figure 2. Relationship between r and T at Gas Flow Rate of 10 SLM and Different Oxygen Concentrations

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图 3 反应速率常数k₄与T的关系

Figure 3. Relationship between Oxidation Rate Constant k₄ and T

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图 4 实验与COMSOL软件模拟计算的r对比

Figure 4. Comparison between Experimental and COMSOL Calculated r

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图 5 实验与COMSOL软件模拟计算的CO浓度对比

Figure 5. Comparison between Experimental and COMSOL Calculated CO Concentrations

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图 6 实验与COMSOL 软件模拟计算的CO₂浓度对比

Figure 6. Comparison between Experimental and COMSOL Calculated CO₂ Concentrations

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图 7 实验与COMSOL软件模拟计算的失重率对比

Figure 7. Comparison between Experimental and COMSOL Calculated Weight Loss Rates

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表 1 国产核级石墨和IG110核级石墨的物理性质对比

Table 1. Properties 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/10⁻⁶
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 石墨氧化腐蚀实验工况

Table 2. Experimental Conditions of Graphite Oxidation Corrosion

实验编号	温度/ ℃	Q_v/ (L·min⁻¹)	O₂浓度/ %	实验编号	温度/℃	Q_v/ (L·min⁻¹)	O₂浓度/ %
1201	500	10	10	1202	500	10	20
1203	550	10	10	1204	550	10	20
1205	600	10	10	1206	600	10	20
1207	650	10	10	1208	650	10	20
1209	700	10	10	1210	700	10	20
1211	750	10	10	1212	750	10	20
1213	800	10	10	1214	800	10	20
1215	900	10	10	1216	900	10	20
1217	1000	10	10	1218	1000	10	20
1219	1100	10	10	1220	1100	10	20
1101	550	20	2.5	1102	550	20	5
1103	600	20	2.5	1104	600	20	5
1105	700	20	2.5	1106	700	20	5
1107	800	20	2.5	1108	800	20	5
1109	900	20	2.5	1110	900	20	5
1111	1000	20	2.5	1112	1000	20	5
1113	1100	20	2.5	1114	1100	20	5

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表 3 石墨氧化腐蚀模型中动力学参数

Table 3. Kinetic Parameters in Graphite Oxidation Corrosion Model

反应	LU W^[2]		拟合结果
反应	A₀/ s⁻¹	E_a0/ (kJ·mol⁻¹·K⁻¹)	A/ (m³·mol⁻¹·s⁻¹)	E_a/ (kJ·mol⁻¹·K⁻¹)
R1	1.14×10⁸	222.5	2.3712×10⁶	222.79
R2	3.27×10⁶	189.1	6.8016×10⁴	189.35
R3	1.24×10⁸	333.6	2.5792×10⁶	334.03
R4	1.30×10⁸	113.0	2.6104×10⁶	137.38

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