Synergy of ruthenium and cobalt in SiO 2-supported catalysts on ethylene hydroformylation

Abstract

Dynamic hydroformylation of ethylene at atmospheric pressure and 150°C has been studied in a fixed bed reactor over ruthenium- and cobalt-containing SiO 2-supported catalysts (1% Ru loading). Any combination of ruthenium and cobalt precursors leads to significant improvement of hydroformylation activity with respect to those of monometallic catalysts. The optimal atomic ratio of Co:Ru is estimated to be 3:1 for ideal catalytic activity. A catalyst derived from Ru 3(CO) 12 and Co 2(CO) 8 is most active. A catalyst derived from metal carbonyls is generally more active than a catalyst prepared from metal salts. Metal chlorides retard the preparation of active catalysts in most cases. The catalysts studied exhibit fairly good catalytic stability. The determined rate enhancement of ethylene hydroformylation suggests a synergy of ruthenium and cobalt, which is understood as catalysis by bimetallic particles or ruthenium and cobalt monometallic particles in intimate contact. The synergy causes high ethylene hydrogenation activity while giving enhanced ethylene hydroformylation activity. Meanwhile, the potential of the ruthenium-based catalysts is evaluated from both catalytic performances and cost by comparison with the corresponding rhodium-based ones.