固体酸催化混合芳烃烷基化制备高沸芳烃
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摘要
混合芳烃与苯乙烯在磺化树脂、杂多酸或无水氯化铝为催化剂、氮气气氛及常压条件下反应制备可用于热载体油使用的高沸芳烃。全馏分混合芳烃含有少量高沸芳烃,对其进行色谱-质谱联用分析,再经精馏分离获得以单环芳烃为主的混合芳烃轻馏分。全馏分混合芳烃为原料时,反应得到310~365℃沸点组分的高沸芳烃质量分数为20%,较原料中高沸芳烃质量分数提高15%。催化混合芳烃轻馏分与苯乙烯反应时,生成沸点在310~365℃的组分达到25%~30%。与其他几种催化剂相比,杂多酸对沸点在310~365℃的组分表现出更好的选择性。对比不同磺化树脂的实验表明,相同反应条件,催化剂的酸量是影响产物中高沸芳烃含量的主要原因。
Sulfonated resin,heteropoly acid,and anhydrous AlCl_3 catalysts were detected to catalytic transformation of mixed aromatics to produce high-boiling aromatics which could be used as the thermal oil at N_2 atmosphere.There were a few of high-boiling aromatics in the whole fraction of mixed aromatics,and qualitatively analyzing the whole fraction of mixed aromatics by GC-MS,then a temperature was determined to rectification separate the monocyclic aromatics which was the main components of the light fraction of mixed aromatics from other dicyclic and polycyclic aromatics according to the analysis result.Feeding the whole fraction of mixed aromatics and styrene,it would obtain as high as 20% high-boiling components, and the content increased by 15% to that of the whole fraction of mixed aromatics.While using the light fraction of mixed aromatics as the feedstock,the increased value boosted into 25%~30%.Heteropoly acid catalysts performed a better selectivity for the products with boiling point between 310~365 ℃ comparing with other catalysts.A series of tests for investigating different acid loaded sulfonated resin catalysts indicated that,the acid density mainly affected the high-boiling aromatics contents in products at the same reaction conditions.
Sulfonated resin,heteropoly acid,and anhydrous AlCl_3 catalysts were detected to catalytic transformation of mixed aromatics to produce high-boiling aromatics which could be used as the thermal oil at N_2 atmosphere.There were a few of high-boiling aromatics in the whole fraction of mixed aromatics,and qualitatively analyzing the whole fraction of mixed aromatics by GC-MS,then a temperature was determined to rectification separate the monocyclic aromatics which was the main components of the light fraction of mixed aromatics from other dicyclic and polycyclic aromatics according to the analysis result.Feeding the whole fraction of mixed aromatics and styrene,it would obtain as high as 20% high-boiling components, and the content increased by 15% to that of the whole fraction of mixed aromatics.While using the light fraction of mixed aromatics as the feedstock,the increased value boosted into 25%~30%.Heteropoly acid catalysts performed a better selectivity for the products with boiling point between 310~365 ℃ comparing with other catalysts.A series of tests for investigating different acid loaded sulfonated resin catalysts indicated that,the acid density mainly affected the high-boiling aromatics contents in products at the same reaction conditions.
引文
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[3]李鹏,魏朝良,张东恒,等.高温导热油发展概述[J].润滑油,2016,31(4):1-5.
[4]苏仁球,张京通,苏惠忠,等.由C10重芳烃渣油制备高温导热油基础油的工艺:中国,103351887[P].2013-10-16.
[5]许志明,张立,赵锁奇,等.催化裂化油浆的分离与化工利用[J].石油炼制与化工,2001,32(9):17-21.
[6]刘福洲,陈俊杰.催化裂解轻油抽出芳烃生产导热油的研究[J].辽宁化工,2002,31(10):437-438.
[7]顾荣魁.高温导热油的研制[J].石油炼制与化工,1981(9):25-28.
[8]赵凤阁,董慧茹,刘国文.联苯苄基化反应合成高温导热油的研究[J].北京化工大学学报:自然科学版,2003,30(1):77-79.
[9]de Angelis A,Amarilli S,Berti D,et al.Alkylation of benzene catalysed by supported heteropolyacids[J].J.Mol.Catal.A:Chem.,1999,146(1/2):37-44.
[10]王犇,孙晓岩.PEG2000对MCM-22分子筛结构特性和催化性能的影响[J].无机盐工业,2008,40(12):33-35,49.
[11]孙学文,赵锁奇,王仁安.[bmim]Cl/Fe Cl3离子液体催化苯与乙烯烷基化的反应机理[J].催化学报,2004,25(3):247-251.
[12]原平方,刘春江.新型硫酸法C4烷基化工艺的模拟[J].石油化工,2015,44(5):543-547.
[13]郝向英,魏景芳,照日格图,等.SO42-/杭锦2#土催化剂的制备及性能研究[J].无机盐工业,2012,44(12):56-58.
[14]Bai X X,Pan L Y,Zhao P,et al.A new solid acid SO4/Ti O2catalyst modified with tin to synthesize 1,6-hexanediol diacrylate[J].Chinese J.Catal.,2016,37(9):1469-1476.
[15]刘伟,于海斌.硅胶负载的铬系催化剂研究进展[J].无机盐工业,2009,41(3):9-12.