Preparation of Corrosion Inhibitor for Self-Diverting Acid and Mechanisms of Corrosion Inhibition
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摘要: 转向酸广泛应用于碳酸盐岩储层酸化酸压，由于黏弹性表面活性剂分子结构特殊，常规缓蚀剂配伍性较差，且缓蚀效率大幅降低。采用1-氯甲基萘、4-乙基吡啶、氯化苄和2,3-环戊烯并吡啶合成了2种吡啶季铵盐缓蚀剂SI-1和SI-2。采用腐蚀仪、流变仪考察了SI-1和SI-2在转向酸中的缓蚀性能及其对转向酸黏度的影响；通过扫描电子显微镜、能谱仪、原子力显微镜和X射线光电子能谱等实验手段，从微观角度分析钢片腐蚀前后表面形貌和化学成分；采用分子动力学模拟方法对缓蚀剂SI-1和SI-2的缓蚀机理进行了探讨。结果表明：合成的2种吡啶季铵盐缓蚀剂在转向酸中的缓蚀性能良好，对转向酸黏度影响小，适用性强，成本低。其中缓蚀剂SI-2性能更优，1%加量下，90 ℃腐蚀速率为1.04 g/(m2·h)，120 ℃腐蚀速率为7.43 g/(m2·h)，VES残酸最终黏度可稳定在190 mPa·s以上，成本可降低20%。加入1%缓蚀剂后钢片表面均未出现明显腐蚀，Fe含量大幅上升，表面粗糙度大幅降低，其中添加缓蚀剂SI-2后，Fe含量从86%上升至94%，Ra从137 nm下降至84 nm。钢片表面均检测到C—N与Organic C=O（羰基），表明存在缓蚀剂吸附膜。分子动力学模拟显示缓蚀机理为：SI-2能隙小，吸附能大，缓蚀剂吸附到钢片表面后可形成致密吸附膜，隔绝腐蚀介质与钢片表面的接触，极大地抑制钢片腐蚀。SI-2在渤海油田和伊拉克米桑油田进行了现场应用，施工效果良好。Abstract: Self-diverting acids are widely used in the acidification and fracturing of carbonate reservoirs. Corrosion inhibitors, because of the special molecular structures of the viscoelastic surfactants, have poor compatibility with other additives and corrosion control efficiency that is quite low. In this study, two pyridine quaternary ammonium salt corrosion inhibitors, SI-1 and SI-2, are synthesized with 1-chloromethylnaphthalene, 4-ethylpyridine, benzyl chloride and 2,3-cyclopentenopyridine. The corrosion control performance and the effects on the viscosity of self-diverting acids of SI-1 and SI-2 were investigated using corrosion tester and rheometer. The morphology and chemical components of steel plates before and after corrosion by acids were analyzed from the microscopic perspective by means of SEM, EDS, atomic force microscope and X-ray photoelectron spectroscopy. The corrosion mechanisms of the two corrosion inhibitors were studied using molecular dynamics simulation. The results of researches show that SI-1 and SI-2 have good corrosion control performance in self-diverting acids, minor effects on the viscosity of the self-diverting acids and wide applicability, and is cost-efficient. Compared with SI-1, SI-2 has better performance. A self-diverting acid treated with 1% SI-2 has corrosion rate at 90 ℃ of 1.04 g/(m2∙h), corrosion rate at 120 ℃ of 7.43 g/(m2∙h), final viscosity of the VES residual acid stabilized at 190 mPa∙s or higher. The cost of treatment can be reduced by 20% with SI-2. After adding 1% corrosion inhibitor in the acid, the surfaces of the steel plates show no obvious corrosion, the Fe content increases greatly, and the surface roughness decreases significantly. With SI-2, the Fe content increases from 86% to 94%, and Ra decreases from 137 nm to 84 nm. In both cases C—N and organic C=O bonds are detected on the surfaces of the steel plates, indicating the existence of the adsorption membranes of the corrosion inhibitors. Molecular dynamics simulation shows the mechanisms of corrosion inhibition are as follows: SI-2 has small energy gaps and high adsorption energy. After being adsorbed on the surfaces of the steel plates, a dense adsorption membrane is produced, isolating the corrosion media and the surfaces of the steel plates, thereby remarkably inhibiting the corrosion process of the steel plates. SI-2 has been used in the Bohai Oilfield and the Missan Oilfield (Iraq) with excellent operation achievement.
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表 2 腐蚀实验数据
缓蚀剂 90 ℃腐蚀速率/g/(m2·h) 120 ℃腐蚀速率/g/(m2·h) 空白 693.12 2012.36 SI-1 3.35 22.56 SI-2 1.04 7.43 
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表 3 试片表面元素含量测试结果
类型 元素含量/% Fe C O N 未腐蚀的N80钢片 94.42 6.59 0.97 0.48 未加缓蚀剂 86.24 5.12 2.45 0.53 添加1% SI-1 93.15 7.03 1.23 0.62 添加1% SI-2 94.16 6.81 1.09 0.60
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表 4 各体系AFM微观形貌的表面粗糙度参数
类型 表面粗糙度参数 Ra Ah Rmax 未腐蚀的N80钢片 6 65 149 未加缓蚀剂 137 655 2457 添加1%SI-1 88 382 1375 添加1%SI-2 84 411 1306
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表 5 N80钢片表面化合物的结合能实验数据与标准数据对比
原子价态 标准值/eV 1%SI-1
实验值/eV1%SI-2
实验值/eVFe2O3 FeCl2 C—N Fe2p 710.9 710.4 711.2、710.6 711.1、710.5 O1s 530.2 529.8 530.1 C1s 284 283.7 284.3 N1s 400 400.5 399.8 Cl2s 199 198.5 200.2
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表 6 2种缓蚀剂分子的全局活性参数
参数 缓蚀剂 SI-1 SI-2 EHOMO −4.861 −4.497 ELOMO −2.032 −2.562 χ 3.447 3.530 η 1.415 0.968 μ −3.447 −3.530 σ 0.707 1.033 ∆N 1.255 1.792 ω 4.199 6.436 ∆E 2.869 1.935
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