Selective Hydrogenolysis and Hydrogenation of Furfuryl Alcohol in the Aqueous Phase Using Ru–Mn-Based Catalysts

Abstract

Most biomass derivatives were converted in the aqueous phase due to their high oxygen content, which, however, created a harsh environment for the catalytic reaction. In this work, Ru-based catalysts for the hydrogenation/ hydrogenolysis of furan compounds in the aqueous phase were prepared. Among all the screened catalysts, the Ru−Mn/CNTs (multiwalled carbon nanotubes) catalyst was found to be the best one for the conversion. Also, various factors, including reaction temperature, H 2 pressure, solvent, and catalyst promotor, were studied to tune the catalytic performance of hydrogenation and hydrogenolysis reactions, whereas as high as 80% tetrahydrofurfuryl alcohol (THFA) selectivity and 20% 1,2pentanediol (1,2-PeD) selectivity were obtained over Ru−Mn/CNTs catalysts under different reaction conditions, respectively. Moreover, detailed characterizations were carried out over the relevant catalysts for correlating the catalytic and physicochemical properties.

Hydrogenolysis of Furfuryl Alcohol to 1,2‐Pentanediol Over Supported Ruthenium Catalysts

“…We speculate that the basic sites on MgO, Al 2 O 3 , and CeO 2 may have enhanced the hydrogenolysis of furfuryl alcohol to 1,2‐PeD, which is consistent with previously reported results. [ 10 , 18 , 21 ]…”

“…We speculate that the basic sites on MgO, Al 2 O 3 , and CeO 2 may have enhanced the hydrogenolysis of Metal particle size/ nm [a] Surface area/ m 2 g À furfuryl alcohol to 1,2-PeD, which is consistent with previously reported results. [10,18,21] Finally, we investigated the effect of reaction temperature on the 1,2-PeD selectivity of hydrogenolysis of furfuryl alcohol over Ru/Al 2 O 3 or Ru/MgO in water (Table 6), which were the catalyst/solvent combinations that gave the highest 1,2-PeD selectivity at 403 K. When Ru/Al 2 O 3 was used as the catalyst, the 1,2-PeD selectivity decreased with increasing temperature, whereas the selectivities for cyclopentanol and cyclopentanone increased with increasing temperature. The Ru/Al 2 O 3 catalyst was active for the conversion of furfuryl alcohol to cyclopentanol and cyclopentanone with high selectivity.…”

“…reported that a CeO 2 ‐supported Pt catalyst gives 1,2‐PeD with 65 % selectivity by hydrogenolysis of furfuryl alcohol in water and that water molecules participate in the reaction. [11] Other precious metals such as Rh, [17] Pd, [18] and Ru[ 19 , 20 , 21 ] have also been used for hydrogenolysis of furfural and furfuryl alcohol to afford pentanediols. For example, Date et al.…”

“…[10] Ma et al reported that a CeO 2 -supported Pt catalyst gives 1,2-PeD with 65 % selectivity by hydrogenolysis of furfuryl alcohol in water and that water molecules participate in the reaction. [11] Other precious metals such as Rh, [17] Pd, [18] and Ru [19][20][21] have also been used for hydrogenolysis of furfural and furfuryl alcohol to afford pentanediols. For example, Date et al reported that montmorillonite-supported Pd catalyzes the conversion of furfural to 1,2-PeD with a selectivity of 66 % and that the acidic nature of the support plays an important role in the conversion.…”

In Situ Ruthenium Catalyst Modification for the Conversion of Furfural to 1,2-Pentanediol

“…This route has attracted attention as it can become an alternative to the use of oil-based products for their production [6,7]. Noble metal-based catalysts have been described to be highly efficient to produce these two diols from furfural or its hydrogenated derivatives, Pt- [8][9][10][11][12][13][14] and Ru-based [15][16][17][18][19] catalysts producing mainly 1,2-PeD, and Rh-and Ir-based [20][21][22] catalysts, 1,5-PeD. Cu-based [23][24][25] catalysts produce a mixture of both diols usually needing harsher reaction conditions.…”