Ruthenium catalysts, their production and a process for the preparation of cycloaliphatic polyamines using these catalysts

摘要

Novel ruthenium catalysts (I) additionally contain hydroxides and/or hydrated oxides of cerium and manganese and/or their dehydration products. Claimed prepn. of ruthenium catalysts (not restricted to (I)) involves converting soluble cpds. of Ru, Ce and Mn into insoluble cpds. and opt. post-treating the products. Also claimed is the prepn. of cycloaliphatic polyamines (II) by hydrogenation of the corresp. aromatic amines (III), using (I) (where Ru is in metal or bonded form) as catalyst. (I) has Ru content 0.1-10 wt.% (as the element), and Mn:Ce wt. ratio 0.3-5.1 (as elements). (I) may additionally contain additives, auxiliaries and/or carriers. (I) is prepd. from Ru(NO3)2 and/or RuCl3, Ce(NO3)3 and Mn(NO3)2, using an alkaline cpd. as precipitant. The ppte, is post-treated by filtration, washing out soluble components, heat-treating shaping and/or reducing the Ru component to the metal. Esp. post-treatment involves drying at 120 degrees C then calcining at 200-450 degrees C. (III) is a di- or triaminobenzene deriv. of formula (IIIa), a di-, tri- or tetraamino-naphthalene of formula (IIIc): R1-R4 = H or 1-10C alkyl; R5, R6, R5a, R6a = H or OH, or 1-10C alkyl, 5-10C cycloalkyl or 6-14C aryl (all opt. substd. by OH and/or NH2); n = 1 or 2; m, m1 = 0-2, where m + m1 = at least 2; R7, R8 = H or 1-10C alkyl (pref. the same Me, Et or iPr). Hydrogenation is effected at 100-360 degrees C and 50-100 bar, using 0.005-0.5 g Ru (as metal) per kg of (III).