Gas phase hydroformylation of ethylene using organometalic Rh-complexes as heterogeneous catalysts

Abstract

The heterogeneously catalysed gas phase hydroformylation of ethylene to propionaldehyde was studied over solid RhCl(PPh 3 ) 3 and RhCl(CO)(PPh 3 ) 2 . At 3 bar and 185°C, an active phase formed from RhCl(PPh 3 ) 3 which was different from RhCl(CO)(PPh 3 ) 2 under the reaction conditions studied. The selectivity of RhCl(PPh 3 ) 3 to propanal was much better than that of supported Rhmetal. Thus, solid metal-complexes operated in gas phase reactions clearly hold promise as a new class of heterogeneous catalysts.

Enhancing the activity, selectivity, and recyclability of Rh/PPh3 system-catalyzed hydroformylation reactions through the development of a PPh3-derived quasi-porous organic cage as a ligand

“…Among the various developed catalysts for hydroformylation reactions, the Rh/PPh3 (ligand) system is one of the most efficient catalytic systems and has been widely used in both industry and academic research. For example, the Wilkinson catalyst (RhCl(PPh3)3), which was invented in 1965, played a vital role in the history of catalytic hydroformylations [62,63]; however, the recycling of the Wilkinson catalyst remains a large problem, especially for long-chain olefin hydroformylations, as long-chain aldehydes usually have high boiling points, and the Wilkinson catalyst decomposes easily during distillation. Another well-known case is the biphasic Ruhrchemie/Rhone-Poulenc process, which employs sulfonated phosphine ligand TPPTS (Fig.…”

Study on the Development of High-Performance P-Mo-V Catalyst and the Influence of Aldehyde Impurities on Catalytic Performance in Selective Oxidation of Methacrolein to Methacrylic Acid

“…In addition to the conventional cyanohydrin process for the synthesis of MAA, environmentally friendly routes starting from C 2 or C 4 feedstock are developed. A typical route of the C 2 process is as follows: the hydroformylation of ethylene to propionaldehyde is the first step, then condensation follows with formaldehyde to form methacrolein (MAL), which is then oxidized by oxygen (O 2 ) to MAA [1][2][3]. Selective oxidation of MAL to MAA is an important intermediate step in the synthesis of MMA Keggin-type P-Mo-V based on heteropoly acids (HPAs) and their salts are suitable for the selective oxidation of MAL to MAA [4][5][6][7][8][9].…”

“…The MAL feedstock used to produce MAA in the C 2 process often contains aldehyde impurities, such as formaldehyde and propanal. [1][2][3]. The MAL feedstock containing aldehyde impurities was defined as crude MAL.…”

Direct Transformation of Glycerol to Propanal using Zirconium Phosphate‐Supported Bimetallic Catalysts

“…[21][22][23][24][25][26] The PA with a reactive formyl group is an important potential intermediate material to produce high value-added chemicals such as rubbers, plastics, paints, and pesticides, which are commercially produced from fossil resources now. [23,[27][28][29] Obviously, to develop selective and sustainable catalytic system for direct transformation of easily available and inexpensive glycerol into a partially hydrogenated product (PA) is extremely attractive and demanded. To the best of our knowledge, the highly selective hydrogenolysis of glycerol into PA has not been disclosed up to now.…”

“…Although the dehydration of 1,2‐PDO to propanal (PA) has also been studied using various types of heterogeneous catalysts, the catalytic activity and selectivity to PA still remains a huge challenge . The PA with a reactive formyl group is an important potential intermediate material to produce high value‐added chemicals such as rubbers, plastics, paints, and pesticides, which are commercially produced from fossil resources now . Obviously, to develop selective and sustainable catalytic system for direct transformation of easily available and inexpensive glycerol into a partially hydrogenated product (PA) is extremely attractive and demanded.…”