苄基萘双喹啉季铵盐型酸化缓蚀剂的合成及性能研究  

Study on Synthesis and Performance of Benzyl Naphthalene Double Quinoline Quaternary Ammonium Salt Type Acidizing Corrosion Inhibitor

作　　者：杨永钊[1] 贺静[1] 李二冬 张志升[1] 李建勋[1] 王军 田海兰 韩薇薇 董三宝 YANG Yongzhao;HE Jing;LI Erdong;ZHANG Zhisheng;LI Jianxun;WANG Jun;TIAN Hailan;HAN Weiwei;DONG Sanbao(Xingzichuan Oil Production Plant of Yanchang Oil Field Co.Ltd.,Yan′an,Shaanxi 717400,China;Yidao Yueda Petroleum Technology Co.,Ltd.,Xi′an,Shaanxi 710065,China;School of Chemistry and Chemical Engineering,Xi′an Shiyou University,Xi′an,Shaanxi 710065,China)

机构地区：[1]延长油田股份有限公司杏子川采油厂,陕西省延安市717400 [2]西安亿道悦达石油科技有限公司 [3]西安石油大学化学化工学院

出　　处：《钻采工艺》2025年第2期169-176,共8页Drilling & Production Technology

基　　金：国家自然科学基金青年项目“输气管线中天然气水合物壁面沉积层失稳脱落机制研究”(编号:52204046);陕西省教育厅科研计划项目资助“陕北致密油藏CO_(2)响应清洁压裂液体系构筑及应用基础研究”(编号:24JC076);西安市科技计划项目-高校院所人才服务企业项目“新型耐温耐盐耐油超分子泡排剂体系构筑及泡沫特性调控机制研究”(编号:23GXFW0078)。

摘　　要：为减缓油气井酸化作业过程中酸液对金属的腐蚀,研发高性能的缓蚀剂极其关键。文章用2,6-双(溴甲基)萘和喹啉合成了1,1′-(2,6-二亚甲基萘)二喹啉溴化铵(NPQ),将NPQ与1,4-丁炔二醇、乌洛托品复配得到了一种高效的三元缓蚀剂体系。采用静态失重、电化学等方法研究了三元缓蚀剂体系在20%HCl溶液中对J55钢的缓蚀性能;通过扫描电子显微镜(SEM)/X射线能谱仪(EDS)分析了腐蚀后J55钢表面形貌及元素含量,探讨了NPQ在J55钢表面的吸附行为;并采用量子化学计算对缓蚀剂机理进行分析。在90℃下,20%HCl溶液中加入1%三元缓蚀剂后,J55钢的腐蚀速率降为5.54 g/(m^(2)·h),满足SY/T 5405-2019中90℃时低于6 g/(m^(2)·h)的要求。电化学实验表明:该三元缓蚀剂是一种以抑制阳极过程为主的混合型缓蚀剂,通过拟合Langmuir吸附等温线,发现NPQ在J55钢表面的吸附是一个自发的放热过程;量子化学计算表明三元缓蚀剂的最高占据分子轨道(HOMO)部分可以为铁原子的空轨道提供电子形成化学键,最低未占分子轨道(LUMO)部分可以接受铁原子的电子形成反馈键;NPQ与1,4-丁炔二醇、乌洛托品之间存在协同作用,1,4-丁炔二醇和乌洛托品的加入增强了Br原子的福井(Fukui)指数,使其具有更强的供/得电子能力。In order to mitigate the corrosion of metals by acid during oil and gas well acidification,it is crucial to develop high-performance corrosion inhibitors.In this paper,1,1'-(2,6-di(bromomethyl)naphthalene)bisquinolinium bromide(NPQ)was synthesized by reacting 2,6-bis(bromomethyl)naphthalene with quinoline.Then a highly efficient ternary inhibitor system was obtained by compounding NPQ with 1,4-butynediol and urotropine.The corrosion inhibition performance of the NPQ/1,4-butynediol/urotropine ternary inhibitor system for J55 steel in 20%HCl solution was investigated by static weight loss and electrochemical methods.The surface morphology and elemental composition of the corroded J55 steel were analyzed by SEM/EDS.The adsorption behavior of NPQ on the J55 steel surface was discussed,and the corrosion inhibition mechanism was analyzed by quantum chemical calculations.The results showed that the corrosion rate of J55 steel in 20%HCl solution at 90℃with 1%of the NPQ/1,4-butynediol/urotropine ternary inhibitor was 5.54 g/(m^(2)·h),meeting the requirements of the industry standard SY/T 5405-2019≤6 g/(m^(2)·h)at 90℃.The NPQ/1,4-butynediol/urotropine ternary inhibitor is a mixed-type inhibitor that primarily inhibits the anodic process.By fitting the Langmuir adsorption isotherm,it was found that the adsorption of NPQ on the J55 steel surface is a spontaneous exothermic process.Quantum chemical calculations showed that the highest occupied molecular orbital(HOMO)part of the NPQ/1,4-butynediol/urotropine ternary inhibitor can provide electrons to the empty orbitals of iron atoms to form chemical bonds,and the lowest unoccupied molecular orbital(LUMO)part can accept electrons from iron atoms to form feedback bonds.Results supported that there was a synergistic effect between NPQ,1,4-butynediol,and urotropine,and the addition of 1,4-butynediol and urotropine enhanced the Fukui index of the Br atom,giving it stronger electron donating/accepting ability.

关 键 词：酸化缓蚀剂 双子季铵盐 缓蚀性能 量子化学计算 缓蚀机理 

分 类 号：TG174.42[金属学及工艺—金属表面处理] TE39[金属学及工艺—金属学]