The catalytic transfer hydrogenation
(CTH) of glucose to sorbitol
has been studied using a wide collection of different biomass-derived
alcohols and diols as hydrogen donors. Catalytic activity results
reflect the feasibility to conduct this transformation in the presence
of conventional, commercially available Raney Ni-type sponges as catalysts.
Sacrificial diols displayed a superior performance as hydrogen donors
as compared to short-chain alcohols, including secondary alcohols.
Among them, terminal diols such as 1,4-butanediol and 1,5-pentanediol
were revealed as excellent hydrogen donors, providing a high selectivity
in the conversion of glucose into sorbitol. As for the catalysts,
molybdenum promotion provided a very high catalytic activity to sponge
nickel catalysts, even under mild temperature conditions. The transformation
was also studied in a fixed-bed reactor under continuous-flow operation
conditions. Results demonstrate that the catalysts are highly stable
and able to operate for at least 550 h on stream with a high selectivity
in the CTH of glucose to sorbitol.
Sn-USY materials
have been prepared through an optimized post-synthetic
catalytic metalation procedure. These zeolites displayed, upon ion
exchange with alkaline metals, an outstanding activity in the direct
transformation of glucose into methyl lactate, yielding more than
70% of the starting glucose as the target product, and an overall
combined retro-aldol condensation product yield above 95% in a short
reaction time (<4 h). This outstanding catalytic performance is
ascribed to the neutralization of Brønsted acid sites, the consequent
depression of side reactions, and a higher population of tin open
sites in the ion-exchanged Sn-USY zeolites. Reusability tests evidenced
some loss of catalytic activity, partially caused by the closing of
tin sites, although the use of small amounts of water in the reaction
media demonstrated that this deactivation mechanism can be, at least,
partially alleviated.
Long-term liquid phase studies of the activity in the formic acid-mediated hydrogenation of MA to SA were conducted in a fixed bed continuous reactor for two relevant situations: neutralising maleic...
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