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第 35 卷第 8 期 精 细 化 工 Vol.35, No.8
201 8 年 8 月 FINE CHEMICALS Aug. 2018

油田化学品与油品添加剂
减四线馏分油的酯化脱酸反应

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何 柏 1,2 ，刘世成 ，陈昌国 ，崔盈贤 ，廖 建 ，游晓兰
（1. 重庆大学 化学化工学院，重庆 400044；2. 重庆科技学院 化学化工学院，重庆 401331；3. 海洋
石油高效开发国家重点实验室，北京 100027；4. 中海沥青（四川）有限公司，四川 泸州 646000）
摘要：采用浸渍法制备了 ZnO/Al 2 O 3 催化剂，并用于减四线馏分油与乙二醇的酯化脱酸反应。通过 XRD 对不同
灼烧时间制备的催化剂的物相进行了分析，结果表明：较短灼烧时间更有利于活性组分 ZnO 晶体的存在；催化
剂的 NH 3 -TPD 分析表明：灼烧时间为 1 h 的催化剂表面的酸量为 0.415 mmol/g，高于更长灼烧时间催化剂的表
面酸量；考察了催化剂灼烧时间、催化剂用量、乙二醇用量、反应温度和反应时间对脱酸的影响，并对脱酸前
后的馏分油进行 FTIR 表征。结果表明：灼烧时间 1 h 的 ZnO/Al 2 O 3 催化剂具有良好的减压馏分油催化酯化脱酸
活性。优选的实验条件为：减四线馏分油 40 g，催化剂用量为馏分油质量的 2.5%，乙二醇用量为馏分油质量的
4%，反应温度 250 ℃，反应时间 1.0 h，在该条件下，脱酸率达到 92.43%。催化剂重复使用 5 次脱酸率仍可达
到 91.83%，显示出良好的催化活性与稳定性。FTIR 结果显示，减四线馏分油中环烷酸与乙二醇反应转化成为
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酯类，达到了脱酸目的，这也由 CNMR 谱图证实。酯化脱酸后馏分油的酸值大幅度降低，从 2.51 降低到 0.19
mgKOH/g，而其他主要理化性质变化不大。
关键词：减四线馏分油；催化酯化；脱酸；乙二醇；油品添加剂
中图分类号：TQ426.95 文献标识码：A 文章编号：1003-5214 (2018) 08-1408-06

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Deacidification of 4 Vacuum Gas Oil by Catalytic Esterification

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HE Bai , LIU Shi-cheng , CHEN Chang-guo , CUI Ying-xian , LIAO Jian , YOU Xiao-lan
（1. College of Chemical and Chemistry Engineering, Chongqing University, Chongqing 400044, China; 2. College of
Chemical and Chemistry Engineering, Chongqing University of Science and Technology, Chongqing 401331, China;
3. CNOOC Research Institute, Beijing 100027, China; 4. COCC Asphalt (Sichuan) Ltd, Luzhou 646000, Sichuan, China）
Abstract: ZnO/Al 2O 3 catalyst was prepared by an impregnation method and applied in the deacidification
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of 4 vacuum gas oil through the esterification with glycol. The phase structures of the catalysts prepared in
different calcining time were characterized by XRD. It was found that shorter calcining time was more
benefit for active component ZnO. NH 3-TPD was used to measure surface acid amount of the catalysts, the
surface acid amount of catalyst calcined for 1 hour was 0.415 mmol/g, which was higher than that of
catalyst calcined for longer time. The effects of calcining time, catalyst dosage, glycol dosage, reaction
temperature and reaction time on the deacidification were investigated. The vacuum gas oils before and
after the deacidification were characterized by means of FTIR. The results showed that the ZnO/Al 2O 3
calcined for 1 hour exhibited excellent catalytic activity for the esterification. Under the selected reaction
conditions of vacuum gas oil dosage 40 g, the catalyst dosage 2.5% (based on the vacuum gas oil, the same
below), glycol dosage 4.0%, reaction temperature 250 ℃ and reaction time 1.0 h, the acid removal rate
reached 92.43%, that still could reach 91.83% after the catalyst was reused for five times, indicating that the
resultant catalyst had good catalytic activity and stability. The FTIR results revealed that naphthenic acids
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in the vacuum gas oil reacted with glycol into corresponding esters, which was also proved by CNMR, so
the acids were eliminated. Compare with of the vacuum gas oil before the deacidification, the deacidified
oil exhibited low acid value, which decreased from 2.51 to 0.19 KOH/g, while other main physicochemical

收稿日期：2017-07-03; 定用日期：2017-11-22; DOI: 10.13550/j.jxhg.20170532
基金项目：重庆市教委科学技术研究项目（KJ1713342、KJ131405、KJ1601334）
作者简介：何 柏（1980—），男，讲师，博士生，E-mail：hbai2004@126.com。联系人：陈昌国（1960—），男，教授，博士，E-mail：
cgchen@cqu.edu.cn。