Hydrodeoxygenation of Phenol on Ruthenium Supported on Titania:

Influence of Synthesis Parameters

Reyna Rios-Escobedo, O. U. Valdés-Martínez, and J. A. de los Reyes*
Universidad Autónoma Metropolitana-Iztapalapa, Mexico City, 09340 (Mexico)
*jarh@xanum.uam.mx
INTRODUCTION
Bio-oils as obtained from fast pyrolysis of lignocellulosic biomass have great potential for the production of liquid biofuel. However, high amounts of oxygen-containing compounds have been reported in
these oils. Due to this, they exhibit a lower energy density, high corrosivity and instability compared with crude oil [1]. Hydrodeoxygenation (HDO) process is a route to upgrade pyrolysis bio-oils to obtain
fuels and chemicals. Several studies have been carried out to develop HDO catalysts with high activity and selectivity to hydrocarbons. In the last years, supported noble metal catalysts have exhibited a superior HDO
performance owing to their capacity of activating molecular H2 for hydrogenation steps that can lead to the formation of deoxygenated products [2]. Recently, Ru/TiO2 catalyst has showed an increased activity and
selectivity for deoxygenated products from phenolic compounds, compared with Ru on other supports, attributed to the reduction of the support [3]. Newman et al. reported that uncalcined Ru/TiO2 catalysts showed
high activity and selectivity to deoxygenated products of all the catalysts screened in the HDO of phenol [4]. However, as reported widely, the performance of Ru/TiO2 catalysts could be affected by the metal
precursor. The use of chloride precursor has been related to positive effect on selectivity to benzene due to residual chloride species [5]. Therefore, the use of two different ruthenium precursors was explored and the
effect of the step of calcination was studied in this work.

MATERIALS AND METHODS

Ru/TiO2 catalysts containing 1.5 wt.% of ruthenium were prepared by impregnation of TiO2 (P25, Degussa). The Ru(Cl) catalysts were prepared from aqueous solutions of RuCl3∙xH2O (Aldrich), and Ru(NO)
catalysts were impregnated with an aqueous solution of RuNO(NO3)3 (Aldrich). After impregnation, all samples were dried at 393 K. A fraction of Ru(Cl) and Ru(NO) solids were calcined at 573 K for 2 h
in air. Materials were reduced ex-situ before reaction in a 60 mL min-1 H2 flow at 623 K for 2 h. The catalysts were characterized to analyze the reducibility, acidity, and species in the surface by TPR, TPD-NH3, and
XPS. The phenol HDO reactions were carried out in a batch reactor at 593 K and 800 psi H2 pressure. The reaction mixture contained 5.3∙10-3mol L-1 of phenol in n-dodecane and about 50 mg of freshly reduced
catalyst.

RESULTS AND DISCUSSION

CHARACTERIZATION HDO OF PHENOL

Temperature-programmed Reduction X-ray Photoelectron Spectrometry

Table 2. Composition of catalysts reduced at 623 K.
Atomic % Atomic ratios
Catalyst Ti3+ O2-lattice Ru0
0 3+ 4+ 3+ 4+
Ru Ru Ru Ti Ti Ru/Ti
/Ti4+ /Ototal /Run+
Ru(NO) 76.7 0.0 23.3 1.2 98.8 0.012 0.813 3.301 0.058
Ru(NO)-Ca 73.2 0.0 26.8 2.2 97.8 0.023 0.925 2.735 0.037
Ru(Cl) 63.4 9.1 27.5 11.7 88.3 0.132 0.662 1.736 0.084
Ru(Cl)-Ca 77.4 0.0 22.6 14.3 85.7 0.166 0.654 3.422 0.025
a
Calcined at 573 K before reduction.
Figure 4. Catalytic activity in hydrodeoxygenation of phenol at 593 K and 5.5 MPa.
XPS results show that Ru species are mainly in a reduced state.
The calcination step reduces the Ru/Ti ratio probably due to an
increase of ruthenium particle size.

Figure 1. TPR profiles of catalysts: a) Ru(NO), b) Ru(NO)-C,

c)Ru(Cl), d) Ru(Cl)-C.
Figure 5. Reaction network for the hydrodeoxygenation of phenol over Ru/TiO2 catalysts.
NH3-TPD
The results of the NH3-TPD are shown in the Table 1.
When Ru(NO) was calcined the number of weak and
medium acid sites was reduced. On the other hand, the
acid sites formed by the interaction of the chloride
ions (derived from the Ru precursor used) with the
surface of the support were promoted by a calcination
step. Figure 2. The effect of the calcination step.

Table 1. Concentration of acid sites for catalysts reduced at 623 K.

Acid sites (µmol NH3 g-1)* Figure 6. Selectivity at 30 % phenol conversion.

Catalyst
Weak Medium Strong
Ru(NO) 58 74 5 CONCLUSION
Ru(NO)-C 45 71 32 The calcination step has a negative effect on the activity of the catalyst due to
Ru(Cl) 38 45 3 sintering of metal particles. The use of different metal precursor has an effect on
Ru(Cl)-C 36 60 37 titania supported catalysts due to the presence of Cl- ions in the support that favors the
*Desorption temperature <523 K:weak, 523-673 K: medium, and >673 K: formation of defects on the surface (oxygen vacancies and Ti3+) compared to the
strong.
nitrate-prepared solids. The oxygen vacancies sites in combination with ruthenium
Figure 3. The role of defects on the surface of TiO2.
sites improving the selectivity to deoxygenated products in the HDO of phenol.

ACKNOWLEDGMENT REFERENCES
We acknowledge to CONACYT-Mexico for the finantial support 1.Huber, G.W., Iborra, A.S., and Corma, A. Chem. Rev. 2, 4044 (2006).
(616506). 2. De Souza P.M., Nie, L., Borges, L.E.P., Noronha, F., and Resasco, D.E. Catal. Lett. 144, 2005 (2014).
We also acknowledge to CNyN-UNAM for XPS analysis. 3. Boonyasuyat, S., Omotoso, T., Resasco, D.E., and Crossley, S.P. Catal. Lett. 143,783 (2013).
4. Newman, C., Zhou, X., Goundie, B., Ghampson, I.T., Pollock, R.A., Ross, Z., Wheeler, M.C., Meulenberg, R.W., Austin,R.N., and Frederick, B.G. Appl. Catal.A 477, 64 (2014).
5. Wildschut, J., Mélian-Cabrera,I. and Heeres,H.J. Appl. Catal. B 99, 298 (2010).