摘要
采用浸渍法制备了Zn O/Al2O3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Zn O晶体的存在;催化剂的NH3-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Zn O/Al2O3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酯类,达到了脱酸目的,这也由13CNMR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0.19mg KOH/g,而其他主要理化性质变化不大。
Zn O/Al2 O3 catalyst was prepared by an impregnation method and applied in the deacidification of 4 th 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 Zn O. NH3-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 Zn O/Al2 O3 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 in the vacuum gas oil reacted with glycol into corresponding esters, which was also proved by 13 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 physicochemicalproperties varied little.
作者
何柏
刘世成
陈昌国
崔盈贤
廖建
游晓兰
HE Bai;LIU Shi-cheng;CHEN Chang-guo;CUI Ying-xian;LIAO Jian;YOU Xiao-lan(College of Chemical and Chemistry Engineering,Chongqing University,Chongqing 400044,China;College of Chemical and Chemistry Engineering,Chongqing University of Science and Technology,Chongqing 401331,China;CNOOC Research Institute,Beijing 100027,China;COCCAsphalt（Sichuan）Ltd,Luzhou 646000,Sichuan,China)
出处
《精细化工》
EI
CAS
CSCD
北大核心
2018年第8期1408-1413,共6页
Fine Chemicals
基金
重庆市教委科学技术研究项目(KJ1713342、KJ131405、KJ1601334)~~
关键词
减四线馏分油
催化酯化
脱酸
乙二醇
油品添加剂
4th vacuum gas oil
catalytic esterification
deacidification
glycol
oil additives
