金属卟啉催化丙烯环氧化的助剂与工艺研究

Research on auxiliaries and process of propylene epoxidation catalyzed by metalloporphyrin

研究了多种金属络合剂助剂对金属卟啉催化丙烯环氧化反应的影响以及相关反应条件筛选。结果表明,羟基对反应活性的影响明显,磷酸三丁酯为较优的助剂。考察了催化剂种类、催化剂浓度、反应温度、氧气进气速率、烯醛摩尔比和溶剂量对反应结果的影响。结果表明,以Fe(p-CH3) TPPCl为催化剂,在Fe(p-CH3) TPPCl浓度为1. 2×10-5mol/L、进气速率为0. 1 L/min、丙烯用量为10 L、烯醛摩尔比为1∶1. 15、反应温度为100℃、溶剂用量为210 m L、反应时间为0. 5 h的条件下,丙烯转化率为26. 7%,环氧丙烷收率为25. 6%,选择性为95. 9%。

The effects of several auxiliaries on epoxidation of propylene over metalloporphyrin are investigated,and related reaction conditions are screened out. It is indicated that hydroxyl group has a significant effect on the reactivity and tributyl phosphate is a better auxiliary.Influences of catalyst type,catalyst concentration,reaction temperature,oxygen intake rate,molar ratio of aldehyde to propylene and solvent amount are investigated,indicating the appropriate reaction conditions as follows: Fe( p-CH3) TPPCl is used as catalyst with a concentration of 1. 2×10-5 mol·L-1,oxygen intake rate is 0. 1 L·min-1,the dosage of propylene is 10 L,n( propylene) ∶n( aldehyde) = 1 ∶1. 15,100℃,210 m L solvent is used and the reaction spends 0. 5 h. Under these conditions,the conversion rate of propylene can reach 26. 7%,the yield of propylene oxide can reach 25. 6% with selectivity of 95. 9%.