摘要
研究了以离子交换法制备的分子筛负载钌及钌双金属催化剂催化。α-烯烃氢甲酰化反应的催化性能。考察了反应溶剂、分子筛、α-烯烃及其它金属对负载钌催化剂的催化性能影响,对Ru/Co/NaX催化剂考察了负载量、用量及反应时间的影响。使用ZSM-5分子筛载体、碱性DMF和吡啶为溶剂有利于提高催化剂的活性和选择性,含Rh和Sn的双金属催化剂活性和选择性很高,FT-IR特征吸收谱图证实,催化剂于反应条件下转变成Ru_x(CO)_Y/分子筛形式,既含有端羰基又含有桥羰基,其中桥羰基可能是氢甲酰化活性的主要部分。
The results of α- olefin hydroformylation catalysed by ruthenium and bimetallic catalysts supported on zeolite made by cation-exchange of Na+ in zeolite with Ru3+ in aqueous RuCl3 has been reported. The effects of solvent, zeolite support, α-olefin and another transition metallic ion on ruthenium catalyst supported on zeolite have been examined. With increasing polarity of the solvents, the activity and selectivity of Ru/NaX catalyst on hydroformylation increase. When ZSM-5 zeolite is used as support, electron donor DMF or pyridine as the solvent and cation- exchanging Rh3+ or Sn2+ into NaX zeolite, the ruthenium catalysts supported on zeolite have good activity and selectivity. The ratio of Ru to Co, the amount of the catalyst used and running time affect the activity and selectivity of the bimetallic Ru/Co/NaX catalyst remarkably. Under 200℃ , 6. 0 MPa(CO/H2= 1) Ru/Co/NaX(Ru/Co=4/2) catalyst precarbonylated in toluene has the best activity and selectivity. Catalysts used in various conditions were characterized by FT-IR etc. after reaction. FT-IR spectra show that each of the catalysts contains at least one absorbing peak above 2000 cm-1 and one below it , so it is suggested that Ru/S (S = zeolite support) catalyst has turned into Rux(CO)y/S in the reaction process, which contains both the terminal carbonyl and the bridging carbonyl. By analysis of the results of catalyst characterization, it is suggested that the bridging carbonyl in the Rux(CO)Y/S catalyst may be the main active centre in the hydroformylation processes.
出处
《分子催化》
EI
CAS
CSCD
1992年第1期44-51,共8页
Journal of Molecular Catalysis(China)
基金
国家自然科学基金资助课题
关键词
钌
双金属催化剂
Α-烯烃
醛化反应
Ruthenium, Bimetallic catalysts,α-Olefin, Hydroformylation, ZSM-5 zeolite
