丁二烯调聚经甲辛醚制1-辛烯  

Producing 1-Octene from 1,3-Butadiene via 1-Methoxyoctane

作　　者：王华[1] 张今令[1] 孙承林[1] 刘中民[1] 宛海顺[2] 郝庆新[2] 

机构地区：[1]中国科学院大连化学物理研究所天然气化工与应用催化研究室,辽宁大连116023 [2]中国石油天然气股份有限公司抚顺分公司,辽宁抚顺113001

出　　处：《石油化工》2003年第3期200-204,共5页Petrochemical Technology

摘　　要：丁二烯与甲醇经调聚反应生成2,7-辛二烯甲醚,加氢精制后得到的甲辛醚在γ-Al2O3催化剂作用下裂解生成1-辛烯。在一定的调聚反应条件下,2,7-辛二烯甲醚的精馏收率不小于88%(纯度不小于99%)。以Pd/C为加氢催化剂,2,7-辛二烯甲醚转化率及甲辛醚选择性均达100%。采用γ-Al2O3对甲辛醚裂解制1-辛烯的过程进行考察,结果表明,催化剂的催化性能除与酸强度有关外,与其结构有密切关系,具有较大的孔径和比表面积的γ-Al2O3催化剂是甲辛醚催化裂解的较佳催化剂,高的催化选择性需要较弱的酸中心和较大的孔径。在甲辛醚进料空速1～3h-1、反应温度280～330℃的条件下,甲辛醚单程转化率94%～96%,1-辛烯选择性87%左右,单程收率83%。Octene was prepared via steps of (1)reacting 1,3-butadiene with methanol in presence of Ph 3P,Pd(acac) 2 and CH 3ONa to form 1-methoxy-2,7-octadiene; (2)hydrogenating 1-methoxy-2,7-octadiene in presence of a hydrogenation catalyst to form 1-methoxyoctane and (3)cracking of 1-methoxy- octane to produce 1-octene Yield of 1-methoxy-2,7-octadiene in step(1) was about 88% with purity more than 99% under the conditions of n (Ph 3P)/ n (Pd(acac) 2)/ n (CH 3ONa)/ n (1,3-butadiene)/ n (methanol)=8 54×10 -5 /4 27×10 -5 /5 62×10 -4 /1/2 77, t =70 ℃ and time 1 5 h The rectified 1-methoxy-2,7-octadiene was hydrogenated in step(2) in presence of 0 8%Pd/C under conditions of m (1-methoxy-2,7-octadiene)/ m (catalyst)=500, t =100 ℃ and time 1 h In step(3),a series of γ-Al 2O 3 and improved SiO 2 catalysts were investigated in the process of 1-methoxyoctane cracking to produce 1-octene γ-Al 2O 3 catalyst with large pore size and pore volume possessed high catalytic activity Selectivity was closely correlated with its acidity and pore size Yield of 1-octene and conversion of 1-methoxyoctane on γ-Al 2O 3 catalyst were about 83% and 94%～96% respectively, under the conditions of WHSV=1～3 h -1 , t =280～330 ℃

关 键 词：Γ-AL2O3 丁二烯 调聚 甲辛醚 制备 1-辛烯 

分 类 号：TQ221.217[化学工程—有机化工]