427880 Selective Hydrodeoxygenation of Furfural to 2-Methylfuran Using Fe-Cu/Silica Catalyst

Wednesday, November 11, 2015
Exhibit Hall 1 (Salt Palace Convention Center)
Huibo Sheng, Chemical and Biomolecular Engineering, University of Delaware, Newark, DE


Furfural, derived from hemicellulose through hydrolysis and dehydration, is as a promising platform chemical for biofuels production. Furfural, however, cannot directly be used as fuel because it is oxygen rich and self-polymerize when exposed to air or light and has to be transformed into a more suitable species. Furfural can be source of numerous derivatives, which can be either substitutes of fossil fuels or be used as fine chemicals. Among these species 2-methylfuran is specially promising as a biofuel or biodiesel additive.

Supported Cu on silica is a mild hydrogenation catalyst that only hydrogenates the carbonyl group of furfural to from furfuryl alcohol. In this report, we described the properties of iron-containing Cu-based catalysts that show much higher reactivity and very high selectivity towards 2-methylfuran. Furthermore, we found that the catalyst pre-activation condition can have a large effect on the selectivity. Catalyst that calcined and pre-reduced at 210 oC will selectively produce furfuryl alcohol, while that pre-reduced at 270 oC will shift the selectivity to 2-methylfuran.

Materials and Methods

Silica supported Cu-Fe catalysts were prepared by incipient wetness co-impregnation method. The copper loading is 1 wt.% and the atomic ratios of Cu/Fe are 1:0, 9:1, 7:1 and 0 : 1. The catalysts will be reduced at a proper temperature before reaction.

The catalysts were tested in a flow micro reactor. Furfural was fed continuously into the reactor using a syringe pump. All the gas transfer lines were heated to ensure a uniform temperature and avoid product condensation. The reaction products were analyzed on line using a gas chromatograph.

Results and Discussion

The reaction network of furfural on Cu is a two-step series reaction from furfural to furfuryl alcohol and then to 2-methylfuran (Scheme 1). We have found that the addition of Fe (0-0.15% w/w) to Cu (1% w/w) could increase the reaction rates by a factor greater than 3 without any loss in selectivity (Figure 1). However if the pre-reduction was performed at a higher temperature (270 oC), a selectivity shift was observed as shown in Table 1. Considering the shift was only applicable to Cu-Fe/SiO2 catalyst instead of Cu, we investigated the reactivity of the 1 wt.% Fe. The results showed that Fe was not very reactive with furfural, but could convert furfuryl alcohol to 2-methylfuran very fast. Temperature programmed reduction profile suggested Cu was fully reduced at 270 oC, while Fe was most likely only partially reduced (a mixture of FeII and FeIII). An in-situ DRIFT study suggested that FeII species were formed on the surface, as indicated by the adsorption of CO. Our further in-situ XANES study confirmed that iron was partially reduced to +2.7, which was found to be responsible for the high hydrogenation performance of the catalyst.

Scheme 1. Series reaction network of furfural

Figure 1.  Catalytic activity of the Cu-Fe/silica catalysts. The Cu loading are all 1% and the atomic ratio of Cu to Fe is as labeled. Reaction conditions: 1 atm, 210 oC, 50 mL/min of H2 flow, 0.1 mL/hr of furfural, mcat = 50 mg.


Table 1. Selectivity shift of the Cu-Fe (7:1)/SiO2


Conversion of furfural

Selectivity of furfuryl alcohol

Selectivity of 2-methryfuran

210 oC pre-reduction: 5% diluted Cu-Fe (7:1)/SiO2

16 %

87 %

6 %

270 oC pre-reduction: 5% diluted Cu-Fe (7:1)/SiO2

16 %

6 %

87 %


2-Methylfuran is an excellent bio-fuel candidate, which is the hydrodeoxygenation product of furfural. This work presented a promising catalyst that can selective convert furfural to 2-methylfuran.


  1. Corma, A., Iborra, S., Velty, A., Chem. Rev. 107, 2411 (2007).
  2. Lange, J.P., van der Heide, E., van Buijtenen, J., Price, R., ChemSusChem 5, 150 (2012).
  3. Sitthisa, S., Sooknoi, T., Ma, Y., Balbuena, P.B., Resasco, D.E., J. of Catal. 277, 1 (2011)

Extended Abstract: File Not Uploaded