乙酰丙酮镍催化乙炔一步合成丙烯酸丁酯工艺的研究  

One-step synthesis of butyl acrylatefrom acetylene catalyzed by Ni(acac)_2

作　　者：李怡鸣 杨先贵[1] 王公应[1] LI Yi-ming;YANG Xian-gui;WANG Gong-ying(Chengdu Institute of Organic Chemistry,Chinese Academy of Sciences,Chengdu 610041,China;University of Chinese Academy of Sciences,Beijing 100049,China)

机构地区：[1]中国科学院成都有机化学研究所,四川成都610041 [2]中国科学院大学,北京100049

出　　处：《天然气化工—C1化学与化工》2018年第6期29-33,共5页Natural Gas Chemical Industry

摘　　要：在乙炔羰基化合成丙烯酸丁酯(BA)的一系列非卤素镍盐的筛选中,发现Ni(acac)_2具有较高的催化活性。在Ni(acac)_2中添加不同乙酰丙酮类盐,发现加入一定量Naacac·H_2O后反应活性明显提高。考察了催化剂配比,正丁醇用量,乙炔和CO初始分压,反应温度和时间对反应的影响。由实验结果可知,最优的工艺条件为:n(Naacac·H_2O)∶n(Ni(acac)_2)=1∶3、反应温度230℃、初始压力4.7MPa,n(乙炔)∶n(正丁醇)∶n(CO)=1∶1.4∶2.1,反应时间1h。该反应条件下丙烯酸丁酯收率为64.4%,选择性为99.2%。此催化剂体系对设备腐蚀性较低,工业前景良好。The effect of non-halogen nickel-based catalysts on the carbonylation of acetylene to butyl acrylate was investigated,and Ni(acac)2 showed relatively higher activity.The effect of other salts of acetylacetonate on Ni(acac)2 also was investigated,and it was found that adding some Naacac·H2O can enhance activity siganificantly.Then the effects of the ratio of Naacac·H2O to Ni(acac)2,n-butano lamount,the initial pressure of acetylene and carbon monoxide,reaction temperature and timewere investigated,and the optimal reaction conditions were determined as follows:Naacac·H2O to Ni(acac)2 molar ratio of 1:3,230℃,initial pressure of 4.7MPa,n(C2H2):n(n-butanol):n(CO)of 1:1.4:2.1 and reaction time of 1 hour.Under above conditions,the yield of butyl acrylate reached 64.4%with a selectivity of 99.2%.The catalyst has low corrosion to metal reaction equipment and bright future in commercial application.

关 键 词：丙烯酸丁酯 乙炔 乙酰丙酮镍 雷帕羰化反应 

分 类 号：TQ225.131[化学工程—有机化工] O643.3[理学—物理化学]