Advances in the aqueous-phase hydroformylation of olefins from a refinery naphtha cut: The effect of monoethanolamine in the catalytic activity of the Rh/TPPTS system

• The aldehydes obtained can substitute toxic additives like TAME and MBTE in gasoline.
• Adding MEA to the catalytic phase increases the solubility of syn-gas in water 27%.
• The addition of MEA results in a 10-fold increase in the reaction rate.
• The amine could coordinate the Rh-centre creating a catalytically more active species.
• With MEA a pilot-scale plant was redesigned to require much smaller reactors.

In the present work we report the effect of monoethanolamine (MEA) in the biphasic hydroformylation of the olefin content in a real light naphtha cut from “El Palito” refinery in Venezuela using the Rh/TPPTS system. It was found that the MEA increased dramatically the solubility of a 1:1 mixture of H2:CO up to 27% compared with pure water which resulted in a 10 fold increase in the reaction rate. There was spectroscopic evidence of the coordination of the MEA to the rhodium centre. This accelerated reaction allowed for the redesign of a pilot-scale naphtha hydroformylation plant with 55% smaller reactors. The aldehydes obtained were predominantly C7 branched with high octane-value, evidencing that the biphasic reaction is a green technological alternative to the toxic additive currently use in gasoline formulations such as TAME and MTBE.

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