高温高压CO2 环境中超级13Cr不锈钢点蚀有限元模拟

doi:10.11902/1005.4537.2023.088

中国腐蚀与防护学报

2024, Vol. 44

Issue (2): 303-311 CSTR: 32134.14.1005.4537.2023.088 DOI: 10.11902/1005.4537.2023.088

研究报告

本期目录 | 过刊浏览

高温高压CO₂ 环境中超级13Cr不锈钢点蚀有限元模拟

凌东¹, 何坤¹, 余靓², 董立谨¹(

), 张华礼³, 李玉飞³, 王勤英¹, 张智⁴

^1.西南石油大学新能源与材料学院成都 610500
^2.国家管网集团西南管道兰成渝输油分公司成都 610000
^3.中国石油西南油气田分公司工程技术研究院德阳 618300
^4.西南石油大学石油与天然气工程学院成都 610500

Finite Element Simulation of Pitting Corrosion of Super 13Cr Stainless Steel in High-temperature and High-pressured CO₂ Containing Artificial Formation Waters

LING Dong¹, HE Kun¹, YU Liang², DONG Lijin¹(

), ZHANG Huali³, LI Yufei³, WANG Qinying¹, ZHANG Zhi⁴

^1.School of New Energy and Materials, Southwest Petroleum University, Chengdu 610500, China
^2.Southwest Pipeline Company Lanzhou–Chengdu–Chongqing Oil Transmission Branch, Chengdu 610000, China
^3.Engineering Technology Research Institute, Southwest Oil & Gasfield Company, CNPC, Deyang 618300, China
^4.School of Petroleum and Gas Engineering, Southwest Petroleum University, Chengdu 610500, China

引用本文:

凌东, 何坤, 余靓, 董立谨, 张华礼, 李玉飞, 王勤英, 张智. 高温高压CO₂ 环境中超级13Cr不锈钢点蚀有限元模拟[J]. 中国腐蚀与防护学报, 2024, 44(2): 303-311.
Dong LING, Kun HE, Liang YU, Lijin DONG, Huali ZHANG, Yufei LI, Qinying WANG, Zhi ZHANG. Finite Element Simulation of Pitting Corrosion of Super 13Cr Stainless Steel in High-temperature and High-pressured CO₂ Containing Artificial Formation Waters[J]. Journal of Chinese Society for Corrosion and protection, 2024, 44(2): 303-311.

全文: PDF(5477 KB) HTML

摘要:

采用腐蚀浸泡实验和有限元模拟研究了超级13Cr不锈钢在高温高压CO₂环境中的点蚀行为，重点分析了腐蚀时间、温度和CO₂分压对点蚀的影响。结果表明：高温高压腐蚀实验与有限元模拟的点蚀深度较为吻合，且平均点蚀深度随着浸泡时间、温度和CO₂分压的增大而增大。有限元模拟可知点蚀坑内部由于阳离子水解使得内部酸化，并且pH随着温度降低和CO₂分压的增加而下降。此外，点蚀坑内Fe²⁺浓度随着腐蚀时间的延长和温度的提高而增加，但CO₂分压对其影响不大。

关键词 ：超级13Cr不锈钢, 点蚀, 有限元模拟, 高温高压

Abstract：

The pitting growth behavior of super 13Cr stainless steel in high-temperature and high-pressured CO₂ containing artificial formation waters was comparatively assessed via immersion corrosion test and finit element simulation, focusing on the effect of corrosion time, temperature and partial pressure of CO₂ on pitting corrosion. The results show that the pitting depth of super 13Cr stainless steel after high-temperature and high-pressure corrosion tests is consistent with that of finite element simulation, and the average pitting depth increases with the increase of immersion time, temperature and CO₂ partial pressure. The finite element simulation shows that the interior of the pit is acidified due to cationic hydrolysis, and the pH value decreases with the decrease of temperature and the increase of CO₂ partial pressure. In addition, Fe²⁺ concentration inside the pit increases with the increase of corrosion time and temperature while the partial pressure of CO₂ has little effect.

Key words： super 13Cr stainless steel pitting finite element simulation high temperature and pressure

收稿日期: 2023-03-27 32134.14.1005.4537.2023.088

ZTFLH:

TG171

基金资助:国家自然科学基金(52001264);中国石油—西南石油大学创新联合体科技合作项目(2020CX040100)

通讯作者: 董立谨，E-mail: ljdong89@163.com，研究方向为油气田材料腐蚀与防护

Corresponding author: DONG Lijin, E-mail: ljdong89@163.com

作者简介: 凌东，男，1996年生，硕士生

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https://www.jcscp.org/CN/10.11902/1005.4537.2023.088 或 https://www.jcscp.org/CN/Y2024/V44/I2/303

表1 腐蚀浸泡实验参数

图1 有限元模型及网格划分

Reaction mechanism	Current density equation	Initial potential V	Initial urrent density^[19] A·m^-2
$F e → F e 2 + + 2 e -$	$I F e = I F e 0 × e 0.735 × E P O L - E F e - E' R T × C H + C H + r e f$ $× e ∆ H R 1 T r e f - 1 T$	-0.684	2.7 × 10^-11
$C r → C r 3 + + 3 e -$	$I C r = I C r 0 × e 0.735 × E P O L - E C r - E' R T × C H + C H + r e f$ $× e ∆ H R 1 T r e f - 1 T$	-0.988	1.7 × 10^-9
$H + + e - → 12 H 2$	$I c o r r = I H_0 × e (E P O L - E H - E') / R T × (C H + C H + r e f)$	-0.224	2.0 × 10^-4
$H 2 O + e - → 12 H 2 + O H -$	$I c o r r = I H 2 O_0 × e (E P O L - E H 2 O - E') / R T$	-1.072	8.0 × 10^-10

表2 点蚀坑初始电位及电流密度

Project	Chemical reaction	Equilibrium constant
CO₂ solubility	$C O 2 (g) ↔ C O 2 (a q)$	$K H = C C O 2 / φ P C O 2$
Hydration reaction	$C O 2 (a q) + H 2 O ↔ H 2 C O 3$	$K = C H 2 C O 3 / C C O 2$
H₂CO₃ dissociation	$H 2 C O 3 ↔ H + + H C O 3 -$	$K 1 = C H + C H C O 3 - C H 2 C O 3$
HCO₃^- dissociation	$H C O 3 - ↔ H + + C O 3 2 -$	$K 2 = C H + C C O 3 2 - C H C O 3 -$

表3 CO2环境下典型的化学反应和平衡常数[20]

Equilibrium coefficient	60^oC	95^oC	150^oC
K_H	1.17 × 10^-2	7.7 1× 10^-3	3.72 × 10^-4
$K H, f$	2.37 × 10^-6	2.00 × 10^-1	2.49 × 10⁵
K₁	4.96 × 10^-4	4.09 × 10^-4	2.97 × 10^-4
$K 1, f$	9.52 × 10⁷	5.39 × 10⁸	4.51 × 10⁹
K₂	7.98 × 10^-9	8.46 × 10^-9	5.70 × 10^-9
$K 2, f$	1.00 × 10⁹	1.00 × 10⁹	1.00 × 10⁹

表4 不同温度下的平衡系数

Species concentration mol·L^-1	60^oC	95^oC	150^oC
CO₂ concentration	3.14 × 10^-1	2.06 × 10^-1	9.95 × 10^-3
H₂CO₃ concentration	8.10 × 10^-4	5.33 × 10^-4	2.57 × 10^-5
HCO $3 -$ concentration	4.20 × 10^-4	4.20 × 10^-4	5.77 × 10^-5
CO $3 2 -$ concentration	3.51 × 10^-9	4.91 × 10^-9	2.49 × 10^-9
pH	3.02	3.14	3.88

表5 本体溶液边界处不同温度下初始条件

Species concentration mol·L^-1	0.1 MPa	1 MPa	2.8 MPa
CO₂ concentration	7.70 × 10^-3	7.59 × 10^-2	2.06 × 10^-1
H₂CO₃ concentration	1.99 × 10^-5	1.96 × 10^-4	5.33 × 10^-4
HCO $3 -$ concentration	4.46 × 10^-5	1.49 × 10^-4	4.20 × 10^-4
CO $3 2 -$ concentration	2.07 × 10^-9	2.35 × 10^-9	4.91 × 10^-9
pH	3.74	3.27	3.14

表6 本体溶液边界处不同压力下初始条件

图2 2.8 MPa CO2分压/95℃条件下浸泡20 d后典型的点蚀形貌

图3 不同时间、温度和CO2分压下的平均点蚀深度

图4 不同时间、温度和CO2分压下点蚀坑深度模拟与实验结果对比

图5 点蚀坑底部pH随时间变化规律

图6 不同温度和CO2分压条件下点蚀坑内溶液pH值随深度变化规律

图7 不同时间、温度和CO2分压对点蚀坑内部离子浓度分布的影响

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