Rh/N-POP多孔材料催化1-辛烯氢甲酰化制壬醛性能研究

Research on catalytic performance of Rh/N-POP porous material for hydroformylation of 1-octene to nonanal

烯烃氢甲酰化反应是合成高碳醇的重要途径。为了合成高效的负载型氢甲酰化催化剂,以4-乙烯基吡啶和二乙烯基苯为单体,2,2-偶氮二异丁腈为引发剂合成了富氮多孔有机聚合物(N-POP),并以N-POP为载体,碘离子进行修饰,负载活性组分铑(Rh)得到了Rh/N-POP催化剂。采用FT-IR、BET、SEM和TEM等对催化剂进行了表征,发现催化剂载体有较大的比表面积和丰富的微孔-介孔结构,铑以尺寸为2.00 nm的纳米颗粒的形式均匀分散在载体内部。在1-辛烯氢甲酰化反应中,考察了不同条件(膦配体、铑负载量、膦铑物质的量比、温度和压力)对催化剂催化性能的影响。结果表明,配体显著提高了反应活性,以三苯基膦作为配体,在铑负载量为2%(质量分数),反应温度为100℃,反应压力为2.0 MPa,膦铑物质的量比为100:1的条件下,1-辛烯转化率高达97.56%,醛的收率为89.48%,催化剂转化频率为780.48 h^(-1)。

Hydroformylation of olefins is an important way to synthesize higher alcohols.In order to prepare efficient supported hydroformylation catalysts,nitrogen-rich porous organic polymers(N-POP)were synthesized by using 4-vinylpyridine and divinylbenzene as monomers and 2,2-azodiisobutyronitrile as initiator.Rh/N-POP catalyst was prepared by using N-POP as carrier,modifying with iodine ion and loading rhodium(Rh)as active component.The catalysts were characterized by FT-IR,BET,SEM and TEM,and it is found that the catalyst support has a large specific surface area and a rich micropore-mesoporous structure.Rhodium is uniformly dispersed in the form of nanoparticles with a size of 2.00 nm.In the catalytic hydroformylation of 1-octene,the effects of different conditions(phosphine ligand,rhodium loading,phosphine-rhodium molar ratio,temperature and pressure)on the reaction were investigated.The results show that the presence of the ligand greatly improves the reaction activity.With triphenylphosphine as ligand,under the conditions of 2%(mass fraction)rhodium loading,100℃ reaction temperature,2.0 MPa reaction pressure and 100:1 molar ratio of phosphine to rhodium,the conversion rate of 1-octene is as high as 97.56%,the yield of aldehyde is 89.48%,and the conversion frequency of the catalyst is 780.48 h^(-1).