新型高温酸化缓蚀剂的制备及性能评价

doi:10.16085/j.issn.1000-6613.2023-1615

化工进展 ›› 2024, Vol. 43 ›› Issue (10): 5712-5722.DOI: 10.16085/j.issn.1000-6613.2023-1615

• 精细化工 • 上一篇

新型高温酸化缓蚀剂的制备及性能评价

王业飞¹(), 王婧¹, 杨震¹, 杨江², 郭雷³

^1.中国石油大学(华东)石油工程学院，山东青岛 266580
^2.辽宁石油化工大学石油化工学院，辽宁抚顺 113001
^3.铜仁学院材料与化学工程学院，贵州铜仁 554300

收稿日期:2023-09-12 修回日期:2023-10-24 出版日期:2024-10-15 发布日期:2024-10-29
通讯作者: 王业飞
作者简介:王业飞（1968—），教授，博士生导师，研究方向为精细油田化学品、调剖堵水、酸化缓蚀剂及化学法提高采收率等。E-mail：wangyf@upc.edu.cn。
基金资助:
国家重点研发计划政府间国际科技创新合作重点专项(2021YFE0107000);国家自然科学基金面上项目(52074339)

Synthesis and performance of a novel acidizing corrosion inhibitor for high temperature reservoirs

WANG Yefei¹(), WANG Jing¹, YANG Zhen¹, YANG Jiang², GUO Lei³

^1.School of Petroleum Engineering, China University of Petroleum (East China), Qingdao 266580, Shandong, China
^2.School of Petroleum Engineering, Liaoning Petrochemical University, Fushun 113001, Liaoning, China
^3.School of Material and Chemical Engineering, Tongren University, Tongren 554300, Guizhou, China

Received:2023-09-12 Revised:2023-10-24 Online:2024-10-15 Published:2024-10-29
Contact: WANG Yefei

摘要/Abstract

摘要：

为了更好地减缓油气田高温酸化下金属的腐蚀，研究出一种耐高温且配方简单的复合酸化缓蚀剂。以喹啉和氯化苄为原料，采用“一锅法”制备得到了一种新型稠杂环季铵盐（BQD）缓蚀主剂。通过添加甲酸、乌洛托品等复配剂，经过单因素失重法优选，得到一种配方简单的新型高温酸化缓蚀剂GS-1，通过电化学测试、表面形貌分析研究其缓蚀性能，采用分子模拟的方法研究BQD的缓蚀机理。结果表明，GS-1缓蚀剂在添加量为3%时，在160℃下盐酸与土酸的酸化环境中，N80钢片的腐蚀速率分别降低至41.63g/(m²·h)、31.94g/(m²·h)，均可达行业标准要求；GS-1缓蚀剂可在N80钢片表面形成一层吸附保护层，属于兼具抑制阳极和阴极反应的混合型缓蚀剂；量子化学计算及分子动力学模拟表明，BQD的缓蚀活性优于常见的苄基喹啉季铵盐缓蚀剂（BQC），同时BQD分子是以共轭平面为基准，与金属基底平行的角度被吸附于界面上，具有更加高效的缓蚀性能。

关键词: 新型稠杂环季铵盐, 缓蚀性能, 高温酸化, 腐蚀, 电化学, 量子化学计算, 分子模拟

Abstract:

In order to better slow down the corrosion of metal under high temperature acidification in oil and gas fields, a compound acidizing corrosion inhibitor with high temperature resistance and simple formula was investigated. A novel fused heterocyclic quaternary ammonium salt (BQD) was prepared by 'one-pot' reaction with quinoline and benzyl chloride as raw materials. A novel high temperature acidizing corrosion inhibitor GS-1 with simple formula was obtained by weight loss method optimization of single factor analysis with synthetic BQD as the main agent, adding formic acid, urotropine and other compound agents. At the same time, its inhibition performance was studied by electrochemical test, surface morphology analysis and quantum chemical calculation. And the inhibition mechanism of BQD was studied by molecular simulation. The results showed that when the dosage of GS-1 corrosion inhibitor was 3%, the corrosion rates of N80 steel sheets in hydrochloric acid and mud acid at 160℃ were 41.63g/(m²·h) and 31.94g/(m²·h), respectively, which were better than the requirements of industry standards. The high temperature inhibitor GS-1 could form an adsorption protective film on the surface of N80 steel sheets, which could inhibit the mixed corrosion inhibitor of anode and cathode reaction at the same time. Quantum chemical calculations and molecular dynamics simulations indicated that the corrosion inhibition activity of BQD was better than that of the common benzylquinoline quaternary ammonium salt corrosion inhibitor (BQC). At the same time, the BQD molecule was based on the conjugated plane and was adsorbed on the interface at an angle parallel to the metal substrate, which had more better inhibition performance.

Key words: novel fused heterocyclic quaternary ammonium salt, corrosion inhibition performance, high temperature acidizing, corrosion, electrochemistry, quantum chemical calculation, molecular simulation

中图分类号:

TQ047.6

王业飞, 王婧, 杨震, 杨江, 郭雷. 新型高温酸化缓蚀剂的制备及性能评价[J]. 化工进展, 2024, 43(10): 5712-5722.

WANG Yefei, WANG Jing, YANG Zhen, YANG Jiang, GUO Lei. Synthesis and performance of a novel acidizing corrosion inhibitor for high temperature reservoirs[J]. Chemical Industry and Engineering Progress, 2024, 43(10): 5712-5722.

图/表 24

图1 BQD的合成反应

图2 检测BQD含量的核磁共振氢谱图

表1 BQD的元素分析

元素	理论值	实测值
C	81.62%	80.99%
H	4.89%	4.71%
N	5.95%	5.89%

图3 BQD的核磁共振氢谱图

图4 BQD的核磁共振碳谱图

图5 BQD的质谱图

图6 不同主剂缓蚀性能对比图

表2 BQD在不同溶剂中的溶解性

溶剂	BQD溶解度/g	溶解性
水	<0.01	难溶
乙腈	6.13	可溶
甲酸	25.46	易溶
乙醇	4.18	可溶
DMF	18.51	易溶
DMSO	13.85	易溶
异丙醇	5.27	可溶

图7 不同类型溶剂对主剂缓蚀性能的影响

图8 主剂含量对缓蚀性能的影响

图9 乌洛托品含量对缓蚀性能的影响

图10 不同腐蚀介质中GS-1的缓蚀性能

图11 不同添加量GS-1缓蚀剂的极化曲线图

表3 极化曲线的拟合参数

缓蚀剂	添加量 /%	b_a/mV·dec^-1	-b_c/mV·dec^-1	i_corr/μA·cm^-2	–E_corr/mV	ΔE_corr/mV	IE /%
空白	0	120.96	133.00	2271.10	428.23	—	—
GS-1	0.5	151.14	220.21	123.87	416.78	11.45	94.55
	1.0	136.99	298.02	93.36	410.57	17.66	95.89
	1.5	132.86	227.90	89.61	416.68	11.55	96.05
	2.0	128.31	203.69	58.56	406.55	21.68	97.42

图12 不同添加量GS-1缓蚀剂的交流阻抗谱

图13 等效电路图

表4 电化学阻抗谱的拟合参数

缓蚀剂	添加量/%	R_s/Ω·cm²	R_p/Ω·cm²	CPE-T/F·cm²	CPE-P
空白	0	0.548	12.61	2.891×10^-4	0.85
GS-1	0.5	0.510	1428.42	1.015×10^-4	0.81
	1.0	0.466	1797.85	1.255×10^-4	0.79
	1.5	0.853	2497.95	1.101×10^-4	0.80
	2.0	0.555	3130.08	1.120×10^-4	0.80

图14 不同环境失重法评价后N80钢片的SEM和EDS图像

图15 BQC的空间几何构型图

图16 BQD的空间几何构型图

图17 BQC与BQD分子结构图

图18 分子动力学模拟图

图19 BQD与乌洛托品复配体系的分子动力学模拟图

表5 BQC和BQD分子的相关模拟数据

缓蚀剂	E_HOMO/eV	E_LUMO/eV	ΔE/eV	μ/D	E_binding/kJ·mol^-1
BQC	-2.455	-1.232	1.223	3.639	323.50
BQD	-4.542	-2.450	2.092	4.419	749.90

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新型高温酸化缓蚀剂的制备及性能评价

Synthesis and performance of a novel acidizing corrosion inhibitor for high temperature reservoirs

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