Towards the upgrading of fermentation broths to advanced biofuels: a water tolerant catalyst for the conversion of ethanol to isobutanol

The conversion of methanol/ethanol mixtures to isobutanol with the pre-catalyst trans-[RuCl2(dppm)2] (1) is tolerant to the addition of water to the system, achieving an isobutanol yield of 36% at 78% selectivity with water concentrations typical of that of a crude fermentation broth.</p

Catalytic conversion of methanol/ethanol to isobutanol – a highly selective route to an advanced biofuel

Catalysts based on ruthenium diphosphine complexes convert methanol/ethanol mixtures to the advanced biofuel isobutanol, with extremely high selectivity (>99%) at good (>75%) conversion via a Guerbet-type mechanism

Control in advanced biofuels synthesis via alcohol upgrading: catalyst selectivity to n ‐butanol, sec ‐butanol or isobutanol

Ruthenium complexes with tetradentate PNNP donor ligands demonstrate a marked change in selectivity compared to analogous bis bidentate PN complexes in Guerbet catalysis, producing mixtures of n‐butanol (17 %), sec‐butanol (14 %) and ethyl acetate (66 %) rather than the usual 90 %+ selectivity to n‐butanol. Tridentate PNP ruthenium complexes such as [Ru(H)(Cl)(CO)(Ph2PCH2CH2NHCH2CH2PPh2)] also produce sec‐butanol and, in optimized conditions (120 °C, 10 mol% NaOEt base), achieve 71 % selectivity to this butanol isomer. The same tri‐ and tetradentate complexes are efficient catalysts for the conversion of methanol/ethanol mixtures to isobutanol (up to 97 % selectivity). In this way, judicious choice of ligand within this general catalyst family allows selectivity to three butanol isomers of interest as fuel molecules