乌洛托品季铵盐缓蚀剂的合成与复配研究

doi:10.11902/1005.4537.2019.037

中国腐蚀与防护学报

2020, Vol. 40

Issue (3): 244-250 DOI: 10.11902/1005.4537.2019.037

研究报告

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乌洛托品季铵盐缓蚀剂的合成与复配研究

邵明鲁¹(

), 刘德新², 朱彤宇², 廖碧朝³

1 中国石油大学油气资源与探测国家重点实验室石油工程教育部重点实验室北京 102249
2 中国石油大学 (华东) 石油工程学院青岛 266580
3 中石化中原石油工程公司井下特种作业公司压裂工程部濮阳 457164

Preparation of Urotropine Quaternary Ammonium Salt and Its Complex as Corrosion Inhibitor

SHAO Minglu¹(

), LIU Dexin², ZHU Tongyu², LIAO Bichao³

1 State Key Laboratory of Petroleum Resources and Prospecting, Key Laboratory of Petroleum Engineering Ministry of Education, China University of Petroleum, Beijing 102249, China
2 School of Petroleum Engineering in China University of Petroleum (East China), Qingdao 266580, China
3 Department of Fracturing Engineering, Zhongyuan Petroleum Engineering Company of Sinopec Group, Puyang 457164, China

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摘要:

以乌洛托品、溴己烷为主要原料，甲醇为溶剂，合成了一种乌洛托品季铵盐缓蚀剂，采用失重法研究了季铵盐缓蚀剂在15% (质量分数) HCl溶液中的缓蚀性能及复配性能，并采用量子化学计算对缓蚀剂机理进行分析，通过红外光谱、SEM对腐蚀后表面进行分析。结果表明，季铵盐缓蚀剂具有良好的缓蚀性能，在15%HCl、90 ℃下，加量0.5% (质量分数) 时，缓蚀率达98.41%，并且与聚乙二醇、KI、丙炔醇复配后协同增效效果较好；量子化学计算表明该季铵盐缓蚀剂分子活性主要分布在分子环上，与乌洛托品相比具有更小的能隙，在Fe表面也具有更大吸附能，因此乌洛托品季铵盐活性更高。表面分析实验进一步验证了该缓蚀剂分子在QT-800钢片表面形成一层吸附膜。

关键词 ：合成, 乌洛托品, 缓蚀剂, 复配, 量子化学计算

Abstract：

A new type of urotropine quaternary ammonium salt as corrosion inhibitor was synthesized through nucleophilic reaction with urotropine and bromohexane as raw materials, while methanol as solvent. Then, the corrosion inhibition effect of quaternary ammonium salt for QT-800 steel in 15% (mass fraction) HCl solution was assessed by mass loss measurements, IR spectrometer and SEM. The mechanism of corrosion inhibition was studied by quantum chemical density functional theory. The results indicated that the quaternary ammonium salt has good corrosion inhibition performance, when urotropine quaternary ammonium salt of 0.5% (mass fraction) was added into 15%HCl solution at 90 ℃, the inhibition efficiency for QT-800 steel could reach up to 98.41%. The complexes of the urotropine quaternary ammonium salt with polyethylene glycol, potassium iodide and propynol were prepared respectively, and they all showed good performance in corrosion inhibition. Quantum chemical parameters indicates that the chemical activity of the urotropine quaternary ammonium salt is mainly distributed on the molecular ring, which has a smaller energy gap than the urotropine, and a larger adsorption energy on the iron surface. Therefore, the reactivity of urotropine quaternary ammonium salt is higher than that of urotropine. The results of IR spectrum and SEM analysis reveal that the urotropine quaternary ammonium salt molecules could adsorb on the surface of QT-800 steel during the corrosion test in HCl solution.

Key words： synthesis urotropine corrosion inhibitor complex quantum chemical calculation

收稿日期: 2019-03-19

ZTFLH:

TG174.42

通讯作者: 邵明鲁 E-mail: minglushao@163.com

Corresponding author: SHAO Minglu E-mail: minglushao@163.com

作者简介: 邵明鲁，男，1991年生，博士生

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引用本文:

邵明鲁, 刘德新, 朱彤宇, 廖碧朝. 乌洛托品季铵盐缓蚀剂的合成与复配研究[J]. 中国腐蚀与防护学报, 2020, 40(3): 244-250.
Minglu SHAO, Dexin LIU, Tongyu ZHU, Bichao LIAO. Preparation of Urotropine Quaternary Ammonium Salt and Its Complex as Corrosion Inhibitor. Journal of Chinese Society for Corrosion and protection, 2020, 40(3): 244-250.

链接本文:

https://www.jcscp.org/CN/10.11902/1005.4537.2019.037 或 https://www.jcscp.org/CN/Y2020/V40/I3/244

表1 缓蚀剂加量对缓蚀性能的影响

图1 表面活性剂加量与腐蚀速率的关系

图2 增效剂加量与腐蚀速率的关系

表2 正交试验结果与分析

图3 最高占有轨道及最低空轨道的0.03 a.u.等值面图形

图4 分子动力学模拟中缓蚀剂分子在Fe表面达到平衡的状态图

图5 腐蚀后钢片表面与乌洛托品、溴己烷的红外谱图

图6 QT-800钢片在有、无缓蚀剂的15%HCl溶液中腐蚀4 h后的表面形貌

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