Supported metal complex catalysts

doi:10.1016/0304-5102(75)80003-4

Journal of Molecular Catalysis

Volume 1, Issue 1, September 1975, Pages 13-25

https://doi.org/10.1016/0304-5102(75)80003-4 Get rights and content

Abstract

Metal complexes supported on porous solids have been found to be active catalysts for hydrocarbon conversion reactions, both in the presence and absence of a solubilizing liquid phase. Four of the metal complexes were more active when dissolved in a liquid phase: an isomerization catalyst, RhCl₃; three hydroformylation catalysts, (Pφ₃)₂RhCOCl, (Asφ₃)₂RhCOCl and Co₂(CO)₆ (PBu₃)₂. For the hydrogenation catalyst (Pφ₃)₃ RhCl, however, the supported solid catalyst was appreciably more active than its supported liquid-phase counterpart. An active supported liquid-phase catalyst can be made from almost any type of non-volatile catalyst solution, provided that the reactants and products are gases at reaction conditions.

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Selective hydrogenation of cinnamaldehyde (CAL) to cinnamyl alcohol (COL) has been investigated with supported liquid-phase catalysts (SLPC), which contain Ru–TPPTS complexes in water film supported on a porous silica gel, in organic solvent (toluene). It was shown that COL can be mainly produced with small quantities of hydrocinnamaldehyde (HCAL) and hydrocinnamyl alcohol (HCOL). The influence of various reaction and catalyst preparation parameters on the overall rate of reaction and the product selectivity have been examined. In addition, liquid-phase adsorption of CAL on water-loaded silica samples has also been measured. It is believed that the hydrogenation of CAL to COL occurs at the interface between the water film and the organic solvent while that to HCAL at the interface between silica, water, and toluene. The hydrophilic nature of the CO bond of CAL is significant for the selective formation of COL at the water/toluene interface, to which polar CO bonds of CAL molecules are pointing. The product, COL, also has a polar OH group, and so it is difficult for COL to be hydrogenated to HCOL at this interface. At the other silica/water/toluene interface, CAL molecules may be adsorbed with their CC bonds as well, which enables the hydrogenation to HCAL. On recycling of SLPC, its activity and COL selectivity decrease. Both oxygen dissolved in toluene and change of active Ru complexes in the water film are responsible for the decrease of catalytic activity, and the change of the state of dispersion of the water film is significant for the decrease of COL selectivity.
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Citation Excerpt :
An extensive review of SLPCs was given by Villadsen and Livbjerg (1978). SLPC research started in 1930 and was continued by Rony (1969), Rony and Roth (1968, 1975/1976), Scholten and van Hardeveld (1983), Abed and Rinker (1973), Datta and Rinker (1985), Datta, Savage, and Rinker (1985a), Datta, Rydant, and Rinker (1985b), Hoffmeister and Hesse (1990) and Meyer, Rickers, and Hesse (1994), among others. Reilly and Lerou (1998) reviewed the application of SLPCs to selective oxidation examples.
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¹: Present address: Virginia Polytechnic Institute and State University, Blacksburg, Virginia 24061 (U.S.A.)

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Supported metal complex catalysts

Abstract

J. Catal.

J. Catal.

J. Catal.

Chem. Eng. Sci.

Belg. Pat.