首页|超高酸原油中石油酸分子组成表征与腐蚀性预测

超高酸原油中石油酸分子组成表征与腐蚀性预测

Molecular Composition Characterization and Corrosion Prediction of Petroleum Acids in Ultra-High Acid Crude Oil

扫码查看
采用傅里叶变换离子回旋共振质谱法对国内某超高酸原油及其馏分油中的石油酸分子组成进行表征,研究Q345R、lCr5Mo、304L和316L 4种典型炼油装置用材在不同酸值(Total acid number,TAN)油品中的静态腐蚀行为,并构建高温酸腐蚀预测模型.结果表明,TAN为10.403 mg KOH/g、含2个氧原子的O2类石油羧酸是石油酸的主要成分,其中二环、三环环烷酸和单环芳香羧酸含量相对较高.168 h静态挂片腐蚀实验结果表明,4种材质腐蚀速率均随温度升高而增加,高于280 ℃后增加趋势逐渐变缓.不同材质微观腐蚀形貌存在显著差异:Q345R整体呈现均匀腐蚀形态;lCr5Mo表面形成密集蚀坑;304L表面分布少量浅表性腐蚀区;316L仍可见金属光泽.根据腐蚀速率结果,考虑脂肪酸、环烷酸和芳香酸与金属的结合作用,将石油酸分子组成作为腐蚀预测模型的修正项,采用Levenberg-Marquardt(LM)算法拟合模型参数,模型相关系数R2大于0.950,均方根误差RMSE小于0.089,可实现超高酸原油腐蚀性的早期预测,为指导超高酸原油加工装置合理选材、制定检维修计划提供支持.
The molecular composition of petroleum acids in the ultra-high acid crude oil and its fractions were characterized by Fourier transform ion cyclotron resonance mass spectrometry(FT-ICR MS).This aimed to investigate the static corrosion behaviors of four typical steels used in petroleum-refining equipment,such as Q345R,lCr5Mo,304L and 316L,in the oil products with different total acid numbers(TAN),and then establish a prediction model for high temperature acid corrosion.The results show that the TAN of crude oil is 10.403 mg KOH/g,and the O2 class species(petroleum carboxylic acids)with two oxygen hetero-atoms per molecule are the main components of petroleum acids,dominated by bicyclic and tricyclic naphthenic acids and monocyclic aromatic carboxylic acid.The static coupon corrosion test for 168 h indicates that the acid corrosion rates of four steels increase with the increasing of temperature,and the up trends gradually slow down when the temperature is higher than 280 ℃.There is a significant difference in the corrosion micro-morphology of different materials.Q345R presents an overall corrosion morphology and dense pits are formed on the surface of 1Cr5Mo.Only a small amount of superficial corrosion pits are distributed on the surface of 304L,and metallic luster can still be seen on 316L.Based on corrosion rates and considering the combination between aliphatic acid,naphthenic acid,aromatic acid and metals,the molecular composition of petroleum acids is defined as a modification item in corrosion prediction model.The model parameters are fitted by Levenberg-Marquardt(LM)algorithm.For this model,the correlation coefficient R2 is higher than 0.950,and the root mean square error(RMSE)is lower than 0.089.The model can realize the early scientific prediction of corrosion for ultra-high acid crude oil,and thus provide a support for guiding the reasonable material selection and making a check and maintenance plan during the operation of oil processing equipment.

corrosionnaphthenic acidFourier transform ion oyclotron resonance mass spectrometryultra-high acid crude oilprediction

牛鲁娜

展开 >

中石化安全工程研究院有限公司化学品安全国家重点实验室,山东青岛 266000

腐蚀 环烷酸 傅里叶变换离子回旋共振质谱 超高酸原油 预测

中国石油化工股份有限公司科技开发项目

318023-1

2024

石油学报(石油加工)
中国石油学会

石油学报(石油加工)

CSTPCD北大核心
影响因子:0.764
ISSN:1001-8719
年,卷(期):2024.40(3)
  • 14