CO<sub>2</sub>/H<sub>2</sub>S腐蚀体系中咪唑啉季铵盐与3种阳离子表面活性剂间的缓蚀协同效应

doi:10.11902/1005.4537.2019.060

中国腐蚀与防护学报

2020, Vol. 40

Issue (3): 237-243 DOI: 10.11902/1005.4537.2019.060

研究报告

本期目录 | 过刊浏览

CO₂/H₂S腐蚀体系中咪唑啉季铵盐与3种阳离子表面活性剂间的缓蚀协同效应

张晨¹, 陆原²^,³^,⁴, 赵景茂²^,³(

)

1 中国石化销售股份有限公司华南分公司广州 510620
2 北京化工大学材料科学与工程学院北京 100029
3 材料电化学过程与技术北京市重点实验室北京 100029
4 中海油 (天津) 油田化工有限公司天津 300452

Synergistic Inhibition Effect of Imidazoline Ammonium Salt and Three Cationic Surfactants in H₂S/CO₂ Brine Solution

ZHANG Chen¹, LU Yuan²^,³^,⁴, ZHAO Jingmao²^,³(

)

1 South China Branch, Sinopec Sales Co. , Ltd. , Guangzhou 510620, China
2 College of Material Science and Engineering, Beijing University of Chemical Technology, Beijing 100029, China
3 Beijing Key Laboratory of Electrochemical Process and Technology for Materials, Beijing 100029, China
4 CenerTech Oilfield Chemical Co. , Ltd. , Tianjin 300452, China

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摘要:

采用分子动力学模拟技术对CO₂/H₂S腐蚀体系中咪唑啉季铵盐 (IAS) 与3种阳离子表面活性剂间的缓蚀协同效应进行了预测，并通过失重法、极化曲线测试、XPS分析等对预测结果进行验证，同时探讨了缓蚀协同机理。结果表明，IAS与十二烷基三甲基溴化铵 (DTAB)、十四烷基三甲基溴化铵 (TTAB) 间存在较好的缓蚀协同效应，所形成的复合缓蚀剂属于以抑制阳极为主的混合型缓蚀剂；XPS分析结果表明，复合缓蚀剂中起主要缓蚀作用的物质可能为IAS，而表面活性剂则起到填补缓蚀剂膜层缺陷的作用，不同复配体系协同效应的差异，可能与缓蚀剂分子的空间位阻有关。

关键词 ： CO₂/H₂S腐蚀, 碳钢, 缓蚀剂, XPS, 分子动力学模拟, 自由体积分数

Abstract：

The synergistic inhibition effect of imidazoline ammonium salt (IAS) coupled respectively with three cationic surfactants in H₂S/CO₂ brine solution was predicted by molecular dynamic simulation technology. The predicted results were verified for Q235 steel in 3.5%NaCl solution by means of mass loss method, potentiodynamic polarization measurement and XPS analysis. Results show that the combination of IAS with dodecyl trimethyl ammonium bromide (DTAB) or tetradecyl trimethyl ammonium bromide (TTAB) all presents good synergistic inhibition effect. The complex corrosion inhibitors are mixed-type inhibitor. From XPS results, it follows that during the corrosion process, the IAS might mainly play the role in the formation of inhibition film on the Q235 steel surface, while the surfactant could mainly fill in the defects of the forming corrosion inhibition film. Possibly, the difference in synergistic inhibition effect for different complex inhibitors may be related to the steric hindrance of inhibitor molecules.

Key words： CO₂/H₂S corrosion carbon steel corrosion inhibitor XPS molecular dynamic simulation free volume fraction

收稿日期: 2019-05-18

ZTFLH:

TG174

通讯作者: 赵景茂 E-mail: jingmaozhao@126.com

Corresponding author: ZHAO Jingmao E-mail: jingmaozhao@126.com

作者简介: 张晨，男，1989年生，博士生，工程师

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引用本文:

张晨, 陆原, 赵景茂. CO₂/H₂S腐蚀体系中咪唑啉季铵盐与3种阳离子表面活性剂间的缓蚀协同效应[J]. 中国腐蚀与防护学报, 2020, 40(3): 237-243.
Chen ZHANG, Yuan LU, Jingmao ZHAO. Synergistic Inhibition Effect of Imidazoline Ammonium Salt and Three Cationic Surfactants in H₂S/CO₂ Brine Solution. Journal of Chinese Society for Corrosion and protection, 2020, 40(3): 237-243.

链接本文:

https://www.jcscp.org/CN/10.11902/1005.4537.2019.060 或 https://www.jcscp.org/CN/Y2020/V40/I3/237

图1 IAS与3种阳离子表面活性剂的分子结构式

图2 以H2O、H3O+、Cl-、HCO3-或HS-为探针时不同复合缓蚀剂膜层的FFV值随c%IAS的变化曲线

表1 不同缓蚀剂在含CO2/H2S盐水中对Q235钢的缓蚀效果

图3 Q235钢在含有不同缓蚀剂的CO2/H2S共存盐水溶液中测得的极化曲线

表2 通过拟合Q235钢在含有不同缓蚀剂的CO2/H2S共存盐水溶液中测得的极化曲线得到的电化学参数

图4 Q235钢在含有不同缓蚀剂的CO2/H2S共存盐水溶液中浸泡24 h后测得的XPS全谱

图5 Q235钢在含有不同缓蚀剂的CO2/H2S共存盐水溶液中浸泡24 h后测得的N1s高分辨窄谱

表3 通过分析Q235钢在含有不同缓蚀剂的CO2/H2S共存盐水溶液中浸泡24 h后测得的N1s高分辨窄谱得到的参数

图6 CO2/H2S共存盐水溶液中IAS与3种表面活性剂在碳钢表面的成膜机理示意图

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