李俊莉,沈燕宾,李霁阳,王佳,张颖.抗高温高浓盐酸席夫碱基吡啶季铵盐缓蚀剂的研究[J].表面技术,2021,50(9):303-310.
LI Jun-li,SHEN Yan-bin,LI Ji-yang,WANG Jia,ZHANG Ying.Study on the Inhibitor of Schiff Base Pyridine Quaternary Ammonium Salt for Anti-High Temperature and High Concentration Hydrochloric Acid[J].Surface Technology,2021,50(9):303-310
抗高温高浓盐酸席夫碱基吡啶季铵盐缓蚀剂的研究
Study on the Inhibitor of Schiff Base Pyridine Quaternary Ammonium Salt for Anti-High Temperature and High Concentration Hydrochloric Acid
投稿时间:2020-11-22  修订日期:2021-05-13
DOI:10.16490/j.cnki.issn.1001-3660.2021.09.032
中文关键词:  缓蚀剂  席夫碱  吡啶季铵盐  等温吸附  量子化学
英文关键词:corrosion inhibitor  schiff base  pyridine quaternary ammonium salt  isothermal adsorption  quantum chemical
基金项目:陕西延长石油(集团)有限责任公司基础研究项目(ycsy2017JCYJ-A-07);陕西省重点研发计划项目(2017GY-171)
作者单位
李俊莉 陕西省石油化工研究设计院,西安 710054;陕西省石油精细化学品重点试验室,西安 710054 
沈燕宾 陕西省石油化工研究设计院,西安 710054;陕西省石油精细化学品重点试验室,西安 710054 
李霁阳 陕西省石油化工研究设计院,西安 710054;陕西省石油精细化学品重点试验室,西安 710054 
王佳 陕西省石油化工研究设计院,西安 710054;陕西省石油精细化学品重点试验室,西安 710054 
张颖 陕西省石油化工研究设计院,西安 710054;陕西省石油精细化学品重点试验室,西安 710054 
AuthorInstitution
LI Jun-li Shaanxi Research Design Institute of Petroleum and Chemical Industry, Xi’an 710054, China;Shaanxi Provincial Key Laboratory of Petroleum Fine Chemicals, Xi’an 710054, China 
SHEN Yan-bin Shaanxi Research Design Institute of Petroleum and Chemical Industry, Xi’an 710054, China;Shaanxi Provincial Key Laboratory of Petroleum Fine Chemicals, Xi’an 710054, China 
LI Ji-yang Shaanxi Research Design Institute of Petroleum and Chemical Industry, Xi’an 710054, China;Shaanxi Provincial Key Laboratory of Petroleum Fine Chemicals, Xi’an 710054, China 
WANG Jia Shaanxi Research Design Institute of Petroleum and Chemical Industry, Xi’an 710054, China;Shaanxi Provincial Key Laboratory of Petroleum Fine Chemicals, Xi’an 710054, China 
ZHANG Ying Shaanxi Research Design Institute of Petroleum and Chemical Industry, Xi’an 710054, China;Shaanxi Provincial Key Laboratory of Petroleum Fine Chemicals, Xi’an 710054, China 
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中文摘要:
      目的 开发环境友好、抗高温耐浓酸的长效缓蚀剂复配体系。方法 采用红外光谱仪对席夫碱基吡啶季铵盐的分子结构进行表征,采用高温高压腐蚀测定仪、吸附等温模型、动力学参数、扫描电镜和量子化学计算,研究了缓蚀剂对N80的缓蚀性能及其吸附机理。结果 在120、140、160 ℃温度下,随着席夫碱基吡啶季铵盐缓蚀剂(以下简称Shif-PyQA)质量分数的增大,腐蚀速率在低浓度时大幅减小,缓蚀率在低浓度时大幅增加,两者在高浓度时均逐渐趋于平稳。在所测温度范围内,N80在空白溶液中的腐蚀速率远大于在加有Shif-PyQA溶液中的腐蚀速率。随着温度的升高或反应时间的增加,N80的腐蚀速率持续增大,缓蚀率逐渐减小,但减小幅度不大。当温度为120 ℃、Shif-PyQA质量分数为2%时,N80在20%盐酸中的腐蚀速率为28.77 g/(m2.h),缓蚀率为97.97%;当温度为140 ℃、Shif-PyQA质量分数为3%时,N80在20%盐酸中的腐蚀速率为37.12 g/(m2.h),缓蚀率为97.71%;当温度为160 ℃、Shif-PyQA质量分数为4%时,N80在20%盐酸中的腐蚀速率为63.91 g/(m2.h),缓蚀率为96.41%。Shif-PyQA在N80表面的吸附遵循Langmuir等温吸附模型,属于单分子层化学吸附,且N80表面的吸附为自发过程。动力学参数结果表明,添加不同质量分数的Shif-PyQA后,活化能大大增加为74.16 ~88.43 kJ/mol,属化学吸附。量子化学研究表明,席夫碱基吡啶季铵盐(以下简称PyQ-S)分子可与金属形成多中心的稳定吸附,同时PyQ-S分子接受电子的趋势大于供出电子的趋势。结论 Shif-PyQA在温度为120、140、160 ℃时,均可达到SY/T 5405—2019中相关指标要求,对N80具有较好的缓蚀作用。
英文摘要:
      A long-term compound system of environment-friendly, high temperature and concentrated acid resistance was developed. The molecular structure of Schiff base pyridine quaternary ammonium salt was characterized by infrared spectrometer, corrosion and adsorption mechanism of corrosion inhibitor on N80 were studied by high temperature and high pressure corrosion determinator, adsorption isothermal model, kinetic parameters, scanning electron microscope and quantum chemical calculation. The results showed the corrosion rate of N80 decreased sharply and inhibition efficiency increased largely at low mass concentration, and both gradually became stable at high mass concentrations with the increase of Schiff base pyridine quaternary ammonium salt corrosion inhibitor (the following abbreviation was Shif-PyQA) at three temperatures of 120 ℃, 140 ℃ and 160 ℃; the corrosion rate of blank solution was much higher than that of Shif-PyQA solution during the temperature range; the corrosion rate of N80 increased continuously and inhibition efficiency decreased slowly with the increase of temperature and the extension of reaction time, but the decrease was small. When the temperature was 120 ℃ and the mass concentration of Shif-PyQA was 2%, the corrosion rate of N80 was 28.77 g/(m2.h) and the inhibition efficiency was 97.97% in 20% HCl; when the temperature was 140 ℃ and the mass concentration of Shif-PyQA was 3%, the corrosion rate of N80 was 37.12 g/(m2.h) and the inhibition efficiency was 97.71% in 20% HCl; when the temperature was 160 ℃ and the mass concentration of Shif-PyQA was 4%, the corrosion rate of N80 was 63.91 g/(m2.h) and the inhibition efficiency was 96.41% in 20% HCl, the adsorption of Shif-PyQA on N80 surface followed the Langmuir isotherm adsorption model, which belonged to single molecular layer chemical adsorption, and the adsorption on N80 surface was a spontaneous process; the results of kinetic parameters showed that the activation energy was increased to 74.16~88.43 kJ/mol after adding different concentrations of Shif-PyQA, which belonged to chemical adsorption. Quantum chemical researches showed that Schiff base pyridine quaternary ammonium salt (the following abbreviation was PyQ-S) molecules could form a multicenter stable adsorption with metals, and the trend to accept electrons of PyQ-S molecules was greater than that to provide electrons. Shif-PyQA can meet the requirements of the relevant indicators of SY/T 5405—2019, and has a good corrosion inhibition effect on the N80 when the temperature is 120 ℃, 140 ℃, 160 ℃.
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