脂肪醇制备叔胺的新型催化剂的最新进展

对采用脂肪醇和二甲胺一步胺化制备(得率100%)相应的叔胺(烷基二甲基叔胺)的新型催化剂的最新进展进行了论述,对高活性Cu/Ni/Ca/Ba-St胶体催化剂(Cu0/Ni0/Ca0的比为5∶1∶1)和不含镍的Cu/La2O3进行了讨论。由此得出结论:要达到定量制备的关键因素是,通过结合还原钙或更活泼的促进剂,如Ce0和La0,尽可能地增加催化体系的氢解活性,由此形成金属氢化物,在铜/镍的作用下产生活性氢的“自供体系”。这一就地形成金属氢化物的基本功能将可极大地减少催化剂的用量,使铜质量分数减少到2×10-3%,从而极大地降低二甲胺的歧化,增加目的叔胺的选择性。总的来说,观察到在铜/镍固体催化剂以及胶体催化剂作用下,活性氢自供体系的基本功能使充入的大量氢一点都不被消耗掉。

On the advanced concept for the next generation catalytic systems, targeting quantitative synthesis, for the alcohol-based tertiary amine production

The advanced concept for the next-generation catalysts, targeting the quantitative synthesis (a yield of 100%) for the one-step amination of fatty alcohols and Me2NH to the corresponding tertiary amines, RNMe2, is presented, and it was discussed by referring to the highly active Cu/Ni/Ca/Ba-St colloidal catalyst (Cu0/Ni0/Ca0 , 5:1:1, colloid stabilized by barium stearate, most active in the world) and the Cu / La2O3 catalyst, developed by the Chinese group, not containing Ni. It was concluded that the key step to achieve the quantitative synthesis is to increase the hydrogenolysis activity of the catalytic system as much as possible by incorporation of Ca0 or probably more active promoters such as Ce0 and La0 , all of which form the metal hydrides (CaH2, LaH2, CeH2, CeH3), with the Cu/Ni-core's essential function of "The self-supplying system for active hydrogen". This basic concept on the in-situ formation of the metal hydrides will enable a drastic decrease in catalyst concentration to the level of 20 ppm of Cu, resulting in a significant slowing down of the accompanied trans-alkylation of Me2NH to greatly increase the selectivity of the objective tertiary amines RNMe2. The essential function of the self-supplying system for active hydrogen, in which charged bulk hydrogen is not consumed at all is observed, in general, in the Cu/Ni-based solid catalysts as well as in the colloidal catalysts.