含氟羧酸酯-马来酸酐原油降凝剂的合成及性能研究  

Synthesis and property evaluation of fluorine-containing carboxylate-maleic anhydride pour point depressant for crude oil

作　　者：王翔 张国欣 陆原 胡廷 魏强 陈严飞[2] WANG Xiang;ZHANG Guo-xin;LU Yuan;HU Ting;WEI Qiang;CHEN Yan-fei(CNOOC EnerTech Oilfield Chemical Co.,Ltd.,Tianjin 300450,China;China University of Petroleum-Beijing,Beijing 102249,China)

机构地区：[1]中海油(天津)油田化工有限公司,天津300450 [2]中国石油大学(北京),北京102249

出　　处：《现代化工》2024年第7期124-129,共6页Modern Chemical Industry

基　　金：国家自然科学基金(52171285);天津市科技领军企业重大创新(22YDLQGX00020);中海油能源发展科技重大专项(HFZDZX-GJ2021-02)。

摘　　要：为了改善海上原油管输流动效果,以甲基全氟烷基乙基羧酸酯(GMA)和马来酸酐(MA)为单体、偶氮二异丁腈为引发剂合成聚(甲基全氟烷基乙基羧酸酯-马来酸酐)(GM),以其为主剂与乙烯-乙酸乙烯酯共聚物(EVA)复配形成含氟羧酸酯-马来酸酐原油降凝剂,并对GM合成条件、降凝剂降凝效果影响因素、加剂前后原油流变性和微观形态进行评价分析。结果表明,GM合成优化工艺条件为:GMA与MA摩尔比为5∶1、引发剂质量分数为0.6%、反应温度为75℃、反应时间为8 h;GM与EVA间存在协同作用,当w(GM)∶w(EVA)=6∶4、加剂量为400 mg/L时,原油凝点为5.5℃,降凝幅度为13℃;在温度为10℃时,加剂前后原油黏度从562.9 mPa·s降至93.1 mPa·s,降黏率达83.5%,原油屈服值从986.6 Pa降低至68.02 Pa,屈服值下降率达93.1%;加剂前后蜡晶形态由棒针状大聚集体堆叠变为小聚集体分散,加剂对改善原油低温流动状态具有明显效果。In order to improve the flowing effect of offshore crude oil in pipeline transportation,polymethylperfluoroalkyl ethylcarboxylate-maleic anhydride(GM)is made from methylperfluoroalkyl ethylcarboxylate(GMA)and maleic anhydride(MA),and with azodiisobutyronitrile as initiator.GM is taken as main component to compound with ethylene-vinyl acetate copolymer(EVA)to obtain fluorine-containing carboxylate-maleic anhydride pour point depressant for crude oil.The synthesis conditions for GM copolymer,the factors influencing the de-coagulation effect,the rheology and micromorphology of crude oil before and after addition of pour point depressant are evaluated and analyzed.Results show that the optimal synthesis conditions for GM copolymer are as follows:the molar ratio of GMA to MA is 5∶1,the dosage of azodiisobutyronitrile is 0.6 wt.%,reaction temperature is 75℃,and reaction time is 8 h.There exists a synergistic effect between GM and EVA.The freezing point of crude oil declines by 13℃to 5.5℃when w(GM)∶w(EVA)=6∶4 and the dosage of pour point depressant is 400 mg·L^(-1).At 10℃,the viscosity of crude oil after adding pour point depressant decreases to 93.1 mPa·s from 562.9 mPa·s before adding pour point depressant,with a reduction rate of 83.5%,and the yield value of crude oil decreases from 986.6 Pa to 68.02 Pa,with a decrease of 93.1%.Before and after dosing,the wax crystal morphology changes from rod-needle like large aggregate stacking to small aggregate dispersion,and the dosing generates obvious effect on improving the low-temperature flow state of crude oil.

关 键 词：含氟共聚物 降凝剂 协同降凝 流变性 微观结构 

分 类 号：TE39[石油与天然气工程—油气田开发工程] TQ65[化学工程—精细化工]