From molecular level to process design: Co-solvent-free autocatalytic homogeneous hydrogenation of C5-platform chemical furfural to furfuryl alcohol
Year: 2025
Type: article
Abstract: Furfuryl alcohol (FOL) has been considered a valuable biomass-based platform chemical. We developed a Ru(acac)3/1,4-bis(diphenylphoshino)butane-based homogeneous catalyst for the selective conversion of furfural (FAL) to FOL; however, no detailed kinetic study and process modeling have already been performed. We demonstrated that the co-solvent-free Ru(acac)3/1,4-bis(diphenylphosphino)butane-catalyzed selective hydrogenation of FAL to FOL proceeds via an autocatalytic mechanism. It was proven that FOL facilitates the formation of catalytically active Ru-species, as well as the presence of a transfer hydrogenation reaction between FAL and FOL using deuterium-labeling experiments. According to the best of our knowledge, these reactions have not been evidenced under neat conditions. Based on the autocatalytic behavior of the system, a detailed kinetic study was subsequently performed, and a kinetic model was proposed to account for all the important characteristics of the experimental series. The average deviation between the experimental and calculated kinetic data is 3.6%. The corresponding rate coefficients were determined in the temperature range of 413.1–433.1 K, enabling us to calculate the activation enthalpies and entropies for the precatalyst activation, the direct hydrogenation reaction, and the autocatalytic pathway. The corresponding activation parameters were found to be ΔHapp# = 107.4 ± 7.0 kJmol–1 and ΔSapp# = −35.2 ± 16.8 Jmol–1K–1, ΔHapp# = 132.8 ± 7.2 kJmol–1 and ΔSapp# = 32.3 ± 17.1 Jmol–1K–1, ΔHapp# = 116.2 ± 2.0 kJmol–1 and ΔSapp# = 12.0 ± 4.9 Jmol–1K–1, respectively.Applying the kinetic and thermodynamic parameters, a simplified flowsheet was developed to demonstrate the continuous production of FOL from FAL. At 98% product purity, the overall energy needs to obtain 84 kg/h product were calculated to be 84.4 kW for heating and 94.0 kW for cooling, respectively.
Source: Chemical Engineering Journal
Language: English
Subfield: Biomedical Engineering
Field: Engineering
Domain: Physical Sciences
Open Access status: hybrid
Estimated APC paid: $4,830
Funders: Budapesti Műszaki és Gazdaságtudományi Egyetem, European Commission, Nemzeti Kutatási és Technológiai Hivatal, Nemzeti Kutatási Fejlesztési és Innovációs Hivatal, Innovációs és Technológiai Minisztérium, Nemzeti Kutatási, Fejlesztési és Innovaciós Alap, National Research, Development and Innovation Office, National Renewable Energy Laboratory
OpenAlex ID: W4408432762