Synthesis of Quinoline-based Acidizing Corrosion Inhibitor and its Corrosion Inhibition Performance for J55 Steel in HCl Medium
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摘要: 缓蚀剂是酸化工作液的重要组成部分，研发新型高效缓蚀剂一直是酸化作业研究人员的目标之一。采用季铵化反应合成了炔基喹啉季铵盐缓蚀剂（QAS），通过失重法，确定了QAS与3-苯基-2-丙炔-1-醇（PPA）的最佳复配比例；随后，通过电化学测试、扫描电镜测试、吸附热力学分析以及分子动力模拟，研究了QAS-PPA对J55钢的缓蚀性能与缓蚀机理。结果表明：二元复合缓蚀剂QAS-PPA的最佳质量浓度为0.5%，最佳配比为m（QAS）∶m（PPA）=1∶1，在20%HCl环境中，当QAS-PPA总浓度为0.5%时，90 ℃下4 h内，J55钢片的缓蚀率为99.71%；电化学测试与扫描电镜检测结果表明：QAS-PPA是一种抑制阳极为主的混合型缓蚀剂，并且随着缓蚀剂浓度的增加，J55钢表面所形成的保护层越致密，缓蚀性能越好；吸附行为研究结果表明了QAS在J55钢表面的吸附均遵循Langmuir吸附等温线，同时也是自发进行的，属于混合型缓蚀剂；分子动力学模拟结果显示，QAS-PPA在Fe基底表面存在协同吸附作用，能显著增强混合体系与基底的相互作用能及表面聚集密度。Abstract: Corrosion inhibitors are an essential component of acidizing working fluids, and the development of novel high-performance corrosion inhibitors has long been a key objective for researchers in acidizing operations. A novel alkynyl quinoline quaternary ammonium salt corrosion inhibitor (QAS) was synthesized via quaternization reaction. The optimal compounding ratio of QAS and 3-phenyl-2-propyn-1-ol (PPA) was determined through weight loss measurements. Subsequently, the corrosion inhibition performance and mechanism of QAS-PPA on J55 steel were investigated using electrochemical tests, scanning electron microscopy, adsorption thermodynamic analysis, and molecular dynamics simulations. The results showed that the optimal mass concentration of the binary composite corrosion inhibitor QAS-PPA was 0.5% with a mass ratio of m(QAS)∶m(PPA) = 1∶1. Under 20% HCl environment at 90 ℃ within 4 h, the corrosion inhibition efficiency of J55 steel coupons reached 99.71% at a total concentration of 0.5%. Electrochemical tests and scanning electron microscopy revealed that QAS-PPA acts as a mixed-type corrosion inhibitor with predominant anodic inhibition, and the protective layer formed on the J55 steel surface became denser with increasing inhibitor concentration, leading to improved inhibition performance. Adsorption behavior studies indicated that the adsorption of QAS on the J55 steel surface followed the Langmuir adsorption isotherm and was a spontaneous process, characteristic of a mixed-type inhibitor. Molecular dynamics simulations demonstrated that QAS and PPA exhibited synergistic adsorption on the Fe substrate surface, significantly enhancing the interaction energy between the mixed system and the substrate as well as the surface packing density.
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图 7 各体系分子间相互作用能的波动情况
注：（a）为QAS、PPA以及QAS-PPA混合分子整体与Fe基底之间的分子间相互作用，（b）为QAS、PPA以及QAS-PPA混合分子体系中水分子与Fe基底之间的分子间相互作用
表 1 60 ℃条件下极化曲线拟合数据
QAS-PPA
加量/%Ecorr/
mVi/
μA·cm−2−βc/
V·dec−1βa/
V·dec−1ηT/
%0.0 −175 61.25 0.155 0.103 / 0.1 −158 33.88 0.134 0.084 44.68 0.2 −142 29.51 0.149 0.095 51.82 0.3 −136 20.04 0.145 0.114 67.28 0.4 −136 18.41 0.148 0.126 69.94 0.5 −134 7.079 0.153 0.127 88.44 
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表 2 60 ℃电化学阻抗谱拟合数据
QAS-PPA/
%Rs/
Ω·cm2Rp/
Ω·cm2CPE Cdl/
mF·cm−2ηE/
%Q/
Ω−1·cm−2·sn
×10−3n 0.0 2.468 3.250 0.001700 0.97 0.00153027 / 0.1 0.110 46.35 0.000420 0.81 0.00020640 92.99 0.2 0.103 58.79 0.000345 0.78 0.00012621 94.47 0.3 0.102 62.94 0.000294 0.72 0.00007279 94.84 0.4 0.117 90.78 0.000263 0.74 0.00006711 96.42 0.5 0.102 110.5 0.000124 0.69 0.00002420 97.06
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表 3 J55钢试样表面EDS谱图的元素成分
介质 元素含量/% C N O Fe 25 ℃预处理后 2.57 0.01 0.35 97.07 60 ℃未加缓蚀剂 24.35 6.02 6.41 63.22 90 ℃、0.5% QAS-PPA 8.11 0.07 0.72 91.10
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