Synthesis and Property Evaluation of New Double Quaternary Ammonium Salt as Corrosion Inhibitor
摘 要
以乌洛托品和二卤代烃为原料经季铵化反应合成了4种乌洛托品双季铵盐缓蚀剂:溴化1,2-二乌洛托品乙烷、溴化1,4-二乌洛托品丁烷、溴化1,6-二乌洛托品己烷、溴化1,8-二乌洛托品辛烷。采用失重法、电化学方法研究了双季铵盐缓蚀剂在15%(质量分数)HCl溶液中对QT-800钢的缓蚀性能,并采用量子化学计算对缓蚀剂的缓蚀机理进行了分析,通过电子扫描显微镜对QT-800钢的腐蚀表面进行分析。结果表明:双季铵盐缓蚀剂的缓蚀性能随缓蚀剂分子碳链长度的增加而提高,其中溴化1,8-二乌洛托品辛烷具有最好的缓蚀效果,其加量在0.7%~1.0%(质量分数)时,腐蚀速率低于4 g/(m2·h);溴化1,8-二乌洛托品辛烷属于能同时抑制阳极反应与阴极反应的混合型缓蚀剂;缓蚀剂分子的能隙以及它们在铁表面的吸附能均随着缓蚀剂碳链长度的增加而增大,且吸附能远大于水分子吸附能,缓蚀剂分子能够吸附在QT-800钢表面,抑制点蚀的发生。
Abstract
Four kinds of double quaternary ammonium salt corrosion inhibitors-1,2-diullotropine ethane bromide, 1,4-diullotropine butane bromide, 1,6-diullotropine hexane bromide, 1,8-diullotropine octane bromide-were synthesized using urotropine and dihalogenated hydrocarbon as raw materials by quaternary ammonium reaction. The corrosion inhibition performance of double quaternary ammonium salt corrosion inhibitors to QT-800 steel in 15% (mass fraction) HCl was studied by weight-loss method and electrochemical method, the mechanism of corrosion inhibitors was analyzed by quantum chemical calculation, and the surface after corrosion was analyzed by electron scanning microscopy. The results show that the corrosion inhibition performance of double quaternary ammonium salts increased with the increase of carbon chain length of corrosion inhibitor molecule. 1,8-diullotropine octane bromide showed the best corrosion inhibition among four corrosion inhibitors, which had a corrosion rate lower than 4 g/(m2·h) when its dosage was in the range of 0.7%-1.0% (mass fraction). 1,8-diullotropine octane bromide was a mixed inhibitor that inhibits both anodic reaction and cathodic reaction. The energy gaps of the corrosion inhibitor molecules and their adsorption energy on the surface of iron increased with the increase of carbon chain length of corrosion inhibitor, and the adsorption energy was much greater than that of water molecule. So the corrosion inhibitor molecules could adsorb on the surface of QT-800 steel and inhibited pitting corrosion.
中图分类号 TG174.42 DOI 10.11973/fsyfh-201910007
所属栏目 缓蚀剂
基金项目
收稿日期 2019/1/15
修改稿日期
网络出版日期
作者单位点击查看
引用该论文: SHAO Minglu,YUE Xiang. Synthesis and Property Evaluation of New Double Quaternary Ammonium Salt as Corrosion Inhibitor[J]. Corrosion & Protection, 2019, 40(10): 747
共有人对该论文发表了看法,其中:
人认为该论文很差
人认为该论文较差
人认为该论文一般
人认为该论文较好
人认为该论文很好
参考文献
【1】郑家燊,黄魁元. 缓蚀剂科技发展历程的回顾与展望[J]. 材料保护,2000,33(5):11-15.
【2】董家梅,孙绪新. 缓蚀剂防腐及其在石油机械中的应用[J]. 石油机械,2000,28(5):18-21.
【3】王慧龙,郑家燊. 环境友好缓蚀剂的研究进展[J]. 腐蚀科学与防护技术,2002,14(5):275-279.
【4】王英,曹祖宾,孙微微,等. 缓蚀剂的分类和发展方向[J]. 全面腐蚀控制,2009,23(2):24-26.
【5】王彬,杜敏,张静. 油气田中抑制CO2腐蚀缓蚀剂的应用及其研究进展[J]. 腐蚀与防护,2010,31(7):503-507.
【6】张漫路,赵景茂. 缓蚀剂协同效应与协同机理的研究进展[J]. 中国腐蚀与防护学报,2016,36(1):1-10.
【7】FINŠGAR M,JACKSON J. Application of corrosion inhibitors for steels in acidic media for the oil and gas industry:a review[J]. Corrosion Science,2014,86:17-41.
【8】宋伟伟,张静,杜敏. 双季铵盐类缓蚀剂的研究进展[J]. 化工进展,2011,30(4):842-847.
【9】刘东,林修洲,朱想明. 六次甲基四胺对碳钢缓蚀行为的研究[J]. 当代化工,2011,40(2):111-113.
【10】WANG Y,HU J,WANG Y,et al. A new method for preventing corrosion failure:thiourea and hexamethylenetetramine as inhibitor for copper[J]. Bulletin of the Korean Chemical Society,2016,37(11):1797-1811.
【11】HU S Q,JIA X L,HU J C,et al. Quantum chemical analysis on molecular structures and inhibitive properties of imidazoline inhibitors[J]. Journal of China University of Petroleum,2011,35(1):146-150.
【12】胡松青,贾晓林,胡建春,等. 咪唑啉缓蚀剂分子结构与缓蚀性能的量子化学分析[J]. 中国石油大学学报(自然科学版),2011,35(1):146-150.
【13】LASHKARI M,ARSHADI M R. DFT studies of pyridine corrosion inhibitors in electrical double layer:solvent,substrate,and electric field effects[J]. Chemical Physics,2004,299(1):131-137.
【14】GUO L,ZHU S H,ZHANG S T,et al. Theoretical studies of three triazole derivatives as corrosion inhibitors for mild steel in acidic medium[J]. Corrosion Science,2014,87:366-375.
【15】GECE G. The use of quantum chemical methods in corrosion inhibitor studies[J]. Corrosion Science,2008,50(11):2981-2992.
【16】XIA S W,QIU M,YU L M,et al. Molecular dynamics and density functional theory study on relationship between structure of imidazoline derivatives and inhibition performance[J]. Corrosion Science,2008,50(7):2021-2029.
【17】XU B,YANG W Z,LIU Y,et al. Experimental and theoretical evaluation of two pyridinecarboxaldehyde thiosemicarbazone compounds as corrosion inhibitors for mild steel in hydrochloric acid solution[J]. Corrosion Science,2014,78:260-268.
【18】EDDY N O. Experimental and theoretical studies on some amino acids and their potential activity as inhibitors for the corrosion of mild steel,part 2[J]. Journal of Advanced Research,2011,2(1):35-47.
【2】董家梅,孙绪新. 缓蚀剂防腐及其在石油机械中的应用[J]. 石油机械,2000,28(5):18-21.
【3】王慧龙,郑家燊. 环境友好缓蚀剂的研究进展[J]. 腐蚀科学与防护技术,2002,14(5):275-279.
【4】王英,曹祖宾,孙微微,等. 缓蚀剂的分类和发展方向[J]. 全面腐蚀控制,2009,23(2):24-26.
【5】王彬,杜敏,张静. 油气田中抑制CO2腐蚀缓蚀剂的应用及其研究进展[J]. 腐蚀与防护,2010,31(7):503-507.
【6】张漫路,赵景茂. 缓蚀剂协同效应与协同机理的研究进展[J]. 中国腐蚀与防护学报,2016,36(1):1-10.
【7】FINŠGAR M,JACKSON J. Application of corrosion inhibitors for steels in acidic media for the oil and gas industry:a review[J]. Corrosion Science,2014,86:17-41.
【8】宋伟伟,张静,杜敏. 双季铵盐类缓蚀剂的研究进展[J]. 化工进展,2011,30(4):842-847.
【9】刘东,林修洲,朱想明. 六次甲基四胺对碳钢缓蚀行为的研究[J]. 当代化工,2011,40(2):111-113.
【10】WANG Y,HU J,WANG Y,et al. A new method for preventing corrosion failure:thiourea and hexamethylenetetramine as inhibitor for copper[J]. Bulletin of the Korean Chemical Society,2016,37(11):1797-1811.
【11】HU S Q,JIA X L,HU J C,et al. Quantum chemical analysis on molecular structures and inhibitive properties of imidazoline inhibitors[J]. Journal of China University of Petroleum,2011,35(1):146-150.
【12】胡松青,贾晓林,胡建春,等. 咪唑啉缓蚀剂分子结构与缓蚀性能的量子化学分析[J]. 中国石油大学学报(自然科学版),2011,35(1):146-150.
【13】LASHKARI M,ARSHADI M R. DFT studies of pyridine corrosion inhibitors in electrical double layer:solvent,substrate,and electric field effects[J]. Chemical Physics,2004,299(1):131-137.
【14】GUO L,ZHU S H,ZHANG S T,et al. Theoretical studies of three triazole derivatives as corrosion inhibitors for mild steel in acidic medium[J]. Corrosion Science,2014,87:366-375.
【15】GECE G. The use of quantum chemical methods in corrosion inhibitor studies[J]. Corrosion Science,2008,50(11):2981-2992.
【16】XIA S W,QIU M,YU L M,et al. Molecular dynamics and density functional theory study on relationship between structure of imidazoline derivatives and inhibition performance[J]. Corrosion Science,2008,50(7):2021-2029.
【17】XU B,YANG W Z,LIU Y,et al. Experimental and theoretical evaluation of two pyridinecarboxaldehyde thiosemicarbazone compounds as corrosion inhibitors for mild steel in hydrochloric acid solution[J]. Corrosion Science,2014,78:260-268.
【18】EDDY N O. Experimental and theoretical studies on some amino acids and their potential activity as inhibitors for the corrosion of mild steel,part 2[J]. Journal of Advanced Research,2011,2(1):35-47.
相关信息