Tunable HMF hydrogenation to furan diols in a flow reactor using Ru/C as catalyst

Fulignati, Sara; Antonetti, Claudia; Wilbers, Erwin; Licursi, Domenico; Heeres, Hero J.; Galletti, Anna Maria Raspolli

doi:10.1016/j.jiec.2021.04.057

Cited by 31 publications

(30 citation statements)

References 73 publications

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“…A tandem sequence took place through the in-situ conversion of fructose to HMF followed by its subsequent hydrogenation to BHMTHF. [40] On the other hand, although several protocols have been described for the CF hydrogenation of HMF over variety of catalytic systems, [41][42][43][44][45][46][47][48] the design of new CF procedures in this area remains a thrilling option to implement process intensification strategies, address the reaction scale-up, and improve the productivity.…”

Section: Chemsuschemmentioning

confidence: 99%

“…Moreover, since carbon-supported Ru is the most versatile catalyst for processing water-soluble biosourced organic reactants, [48,49] commercial 5 % Ru/C was used throughout this study to make the investigated procedure as easily accessible as possible. The catalyst for batch experiments was supplied by Sigma Aldrich (5 % Ru/C, lot MKBW5890 V) and was thoroughly characterized for its structural, morphological, and acid properties in recent papers by our group; [38,50] a catalyst cartridge system (5 % Ru/C, CatCart®) supplied by ThalesNano Inc. was used for CF tests.…”

Section: General: Solvent and Catalystmentioning

confidence: 99%

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Tuning the Selectivity of the Hydrogenation/Hydrogenolysis of 5‐Hydroxymethylfurfural under Batch Multiphase and Continuous‐Flow Conditions

et al. 2022

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The hydrogenation/hydrogenolysis of 5-hydroxymethylfurfural (HMF) has been carried out either under single (aqueous) phase or batch multiphase (MP) conditions using mutually immiscible aqueous/hydrocarbon phases, 5 % Ru/C as a catalyst, and both with and without the use of trioctylmethyl phosphonium bis-(trifluoro methane) sulfonimide ([P 8881 ][NTf 2 ]) as an ionic liquid (IL). Alternatively, the hydrogenation of HMF was explored in the continuous-flow (CF) mode with the same catalyst. By changing reaction parameters, experiments were optimized towards the formation of three products: 2,5-bis(hydroxy methyl)furan (BHMF), 2,5-bis(hydroxymethyl)tetrahydrofuran (BHMTHF), and 1-hydroxyhexane-2,5-dione (HHD), which were obtained in up to 92, 90, and 99 % selectivity, respectively, at quantitative conversion. In particular, the single (aqueous) phase reaction of HMF (0.2 m) carried out for 18 h at 60 °C under 30 bar of H 2 , allowed the exclusive synthesis of BHMF from the partial (carbonyl) hydrogenation of HMF, while the MP reaction run at a higher T and p (100 °C and 50 bar) proved excellent to achieve only HHD derived from a sequence of hydrogenation/ hydrogenolysis. It is worth noting that under MP conditions, the catalyst was perfectly segregated in the IL, where it could be recycled without any leaching in the aqueous/hydrocarbon phases. Finally, the hydrogenation of HMF was explored in a H-Cube® flow reactor in the presence of different solvents, such as ethyl acetate, tetrahydrofuran, and ethanol. At 100 °C, 50 bar H 2 , and a flow rate of 0.1 mL min À 1 , the process was optimized towards the formation of the full hydrogenation product BHMTHF. Ethyl acetate proved the best solvent.

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Section: Chemsuschemmentioning

confidence: 99%

Section: General: Solvent and Catalystmentioning

confidence: 99%

Tuning the Selectivity of the Hydrogenation/Hydrogenolysis of 5‐Hydroxymethylfurfural under Batch Multiphase and Continuous‐Flow Conditions

et al. 2022

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“…In order to investigate the kinetics of HMF hydrogenation, the presence of mass transfer phenomenon was assessed. On this basis, both internal and external limitations were investigated through the Weisz-Prater and the Mears criterions, respectively, [22,25] considering the reaction performed at 100 °C and 50 bar representative of the system. The Weisz-Prater and Mears parameters were equal to 0.005 and 4.02 × 10 À 7 , respectively (the numerical details regarding the calculation of both Weisz-Prater and Mears parameters are reported in the Supporting Information), from which it is possible to conclude that under the investigated reaction conditions the internal and external mass transfer were negligible.…”

Section: Kinetic Study Of Hmf Hydrogenationmentioning

confidence: 99%

Integrated Cascade Process for the Catalytic Conversion of 5‐Hydroxymethylfurfural to Furanic and TetrahydrofuranicDiethers as Potential Biofuels

et al. 2022

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The depletion of fossil resources is driving the research towards alternative renewable ones. Under this perspective, 5hydroxymethylfurfural (HMF) represents a key molecule deriving from biomass characterized by remarkable potential as platform chemical. In this work, for the first time, the hydrogenation of HMF in ethanol was selectively addressed towards 2,5-bis(hydroxymethyl)furan (BHMF) or 2,5-bis(hydroxymethyl)tetrahydrofuran (BHMTHF) by properly tuning the reaction conditions in the presence of the same commercial catalyst (Ru/ C), reaching the highest yields of 80 and 93 mol%, respectively. These diols represent not only interesting monomers but strategic precursors for two scarcely investigated ethoxylated biofuels, 2,5-bis(ethoxymethyl)furan (BEMF) and 2,5-bis(ethoxymethyl)tetrahydrofuran (BEMTHF). Therefore, the etherification with ethanol of pure BHMF and BHMTHF and of crude BHMF, as obtained from hydrogenation step, substrates scarcely investigated in the literature, was performed with several commercial heterogeneous acid catalysts. Among them, the zeolite HZSM-5 (Si/Al = 25) was the most promising system, achieving the highest BEMF yield of 74 mol%. In particular, for the first time, the synthesis of the fully hydrogenated diether BEMTHF was thoroughly studied, and a novel cascade process for the tailored conversion of HMF to the diethyl ethers BEMF and BEMTHF was proposed.

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“…Regardless of that pitfall, this approach was demonstrated to be preferable to a single-stage process using either Raney Cu or Raney Ni, where a maximum BHMTHF selectivity was observed at 13 % under the identical conditions. Recently, Fulignati et al [76] described the tunable hydrogenation of 5-HMF in a continuous-flow reactor to selectively produce either BHMF or BHMTHF by regulating the contact time [CCT in a unit of (g cat -min) g 5-HMF…”

Section: Flow Catalytic Hydrogenation Of 5-hmf To Bhmthf Using Hetero...mentioning

confidence: 99%

Sustainable Catalytic Transformation of Biomass‐Derived 5‐Hydroxymethylfurfural to 2,5‐Bis(hydroxymethyl)tetrahydrofuran

Truong

Mishra

et al. 2022

ChemSusChem

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Tunable HMF hydrogenation to furan diols in a flow reactor using Ru/C as catalyst

Cited by 31 publications

References 73 publications

Tuning the Selectivity of the Hydrogenation/Hydrogenolysis of 5‐Hydroxymethylfurfural under Batch Multiphase and Continuous‐Flow Conditions

Tuning the Selectivity of the Hydrogenation/Hydrogenolysis of 5‐Hydroxymethylfurfural under Batch Multiphase and Continuous‐Flow Conditions

Integrated Cascade Process for the Catalytic Conversion of 5‐Hydroxymethylfurfural to Furanic and TetrahydrofuranicDiethers as Potential Biofuels

Sustainable Catalytic Transformation of Biomass‐Derived 5‐Hydroxymethylfurfural to 2,5‐Bis(hydroxymethyl)tetrahydrofuran

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