【作者】 王业飞； 胡华友； 战风涛； 丁名臣； 吴佳佳； 孙霜青； 杨震；

【Author】 WANG Ye-fei;HU Hua-you;ZHAN Feng-tao;DING Ming-chen;WU Jia-jia;SUN Shuang-qing;YANG Zhen;School of Petroleum Engineering,China University of Petroleum (East China);School of Chemistry and Chemical Engineering,Huaiyin Normal University;College of Science,China University of Petroleum(East China);Key Laboratory of Marine Environmental Corrosion and Bio-fouling,Institute of Oceanology,Chinese Academy of Sciences;School of Materials Science and Engineering ,China University of Petroleum (East China);

【机构】 中国石油大学(华东)石油工程学院； 淮阴师范学院化学化工学院； 中国石油大学(华东)理学院； 中国科学院海洋研究所海洋环境腐蚀与生物污损重点实验室； 中国石油大学(华东)材料科学与工程学院；

【摘要】 随着国内外高温深井油气藏投入开发,对酸化用缓蚀剂性能提出了新挑战。目前在用的主流酸化缓蚀主剂分为曼尼希碱与杂环碱季铵盐两大类,并大多需复配以高毒的炔醇类、昂贵的碘化物等增效剂来使用,兼具经济高效、耐高温、环境友好等特点的缓蚀主剂仍然匮乏,成为了制约酸化技术发展的瓶颈。本课题组会同国内外多家单位展开联合攻关,聚焦新型酸化缓蚀剂研究:首次报道了在强酸性条件下具有高效缓蚀性能的一类由传统季铵盐缓蚀主剂得到的吲哚嗪衍生物(图1),并取得了系列成果。这一发现跳出了酸化缓蚀主剂品类固有框架,其创新性和应用潜力引起了广泛关注。相关研究以首次合成的一系列新型吲哚嗪衍生物缓蚀性能的"结构——效果"关系与缓蚀机理研究为主线,利用精准合成并提纯得到的系列含吲哚嗪母环的化合物,通过其精细结构与缓蚀性能的关联研究与综合研判,并借此重新梳理了酸化缓蚀剂研究中"结构"与"效果"之间的关联,在分子水平上夯实对缓蚀剂作用机制的认识。同时,深入挖掘缓蚀作用机理以及协同增效机制,充分释放吲哚嗪衍生物作为酸化缓蚀主剂的潜力,为酸化缓蚀剂产品的升级换代提供了一个可供选择的新方向。本研究的关键问题如下:(1)新型吲哚嗪衍生物缓蚀性能与其分子结构的内在联系潜在的缓蚀性吲哚嗪衍生物的结构多种多样(见图2),若没有基于系统理论的指导此类缓蚀剂的开发是必将是效率低下的。因此应当首先研究吲哚嗪衍生物分子中取代基电荷效应、空间构型等因素与其缓蚀能力间的联系,确立缓蚀构效关系,进而实现高效缓蚀衍生物的优化设计与定向合成。(2)腐蚀介质中吲哚嗪衍生物随时间变化的聚集过程高纯度吲哚嗪衍生物的获得为在分子水平上实现缓蚀机理的深刻认识提供了可能。将吲哚嗪衍生物分散到腐蚀介质中后,在不同酸浓度及温度等条件下,某一时刻缓蚀剂分子所呈现的聚集状态、空间构型等均会存在差异,而这些差异将在很大程度上决定着其在金属——溶液界面各个吸附阶段的缓蚀行为。只有辨清这些缓蚀剂分子在游离态阶段、界面吸附阶段等全过程中的细微差异,才能有效的规避影响其缓蚀性能的不利因素,加快相关理论和产品的开发进程。(3)典型缓蚀增效剂对吲哚嗪衍生物的强化成膜影响机制任何一种缓蚀主剂均需辅以恰当的增效剂来进一步提高最终产品的性价比。因此有必要强化对典型缓蚀增效剂与吲哚嗪衍生物间复配协同作用以及增效剂分子对主剂分子吸附成膜过程影响规律的认知,可为此类新型复合缓蚀剂产品的研制提供重要依据。更多还原

【Abstract】 Indolizine dimer derivatives of quinolinium or pyridinium salts(serves as main component of currently used acidizing Corrosion Inhibitors(CIs)) were synthesized respectively through an optimized mild procedure from quinoline and different halides.The inhibition of the new inhibitors for N80 steel were evaluated in concentrated hot HCl by gravimetric and electrochemical analysis,while their corrosion prevention mechanism were studied and stimulated by DFT method.Surface adsorption and thermodynamic aspect of inhibition process were also investigated and discussed.A relatively high yield(>50 %) of the crude products were reported.Inhibition assessment results showed that compared with their precursor quinolinium salts,the dimer derivative can dramatically mitigate the corrosion speed and exhibit considerable inhibition efficiencies even at an extremely low dosage.The results obtained from gravimetric tests,electrochemical methods as well as the surface analysis are in good agreement and confirmed the well-behaved anti-corrosion properties of the derivatives.The inhibition of conventional quinoline salts CIs would get greatly updated after been converted to their indolizine dimer derivatives.This provides a smart solution for exploring innovative acidizing CI with better protection efficiency.The use of inhibitive indolizine derivatives may largely minimize the total amount as well as the total expenses of CIs in acidizing fluids and showing good prospects in replacement of the current main components of acidizing CIs in the near future.更多还原