Hydrodeoxygenation of furfuryl alcohol over Cu/MgAl and Cu/ZnAl catalysts derived from hydrotalcite-like precursors: A reaction for bio-oil upgrading

Abstract

The aqueous phase hydrodeoxygenation (HDO) of furfuryl alcohol over Cu/MgAl and Cu/ZnAl catalysts with different Mg/Al and Zn/ Al molar ratios, were investigated. Mg-Al and Zn-Al mixed oxides derived from hydrotalcites precursors were used as supports, which were impregnated with an aqueous solution of copper nitrate by incipient wetness impregnation. The HDO reaction was carried out in a typical batch reactor at 5 MPa of H 2 and 200 °C for 4 h. Among the catalysts studied, the Cu/MgAl-0.5 catalyst exhibited the higher furfuryl alcohol conversion (86 %) and yield of cyclopentanol (35 %), which is the reaction product with the highest hydrogencarbon (H/C) ratio. With the Cu/MgAl-3 catalyst a high cyclopentanone yield (67 %) was achieved. The results obtained, showed that copper supported on mixed oxides catalysts derived from hydrotalcite precursors are a promising alternative to improve the bio-oil quality.Keywords: Hydrotalcites, cyclopentanol, furfuryl alcohol, copper, bio-oil upgrading. RESUMENSe investigó la hidrodesoxigenación(HDO) del furfuril alcohol sobre catalizadores de Cu/MgAl y Cu/ZnAl con diferentes relaciones molares Mg/Al y Zn/Al. Óxidos mixtos de Mg-Al y Zn-Al derivados de precursores tipo hidrotalcitas se usaron como soporte, los cuales fueron impregnados con una solución acuosa de nitrato de cobre, mediante el método de impregnación húmeda. La reacción de hidrodesoxigenación (HDO) se realizó en un reactor tipo batch a 5 MPa de H 2 y 200 °C por 4 h. Entre los catalizadores estudiados, el catalizador de Cu/MgAl-0.5 exhibió la más alta conversión del furfuril alcohol (86 %) y rendimiento hacia ciclopentanol (35 %), el cual es el producto de reacción con mayor relación hidrógeno-carbono (H/C). Con el catalizador de Cu/MgAl-3 se logró un alto rendimiento hacia ciclopentanona (67 %). Los resultados obtenidos, mostraron que los catalizadores de óxidos mixtos derivados de precursores tipo hidrotalcitas son una alternativa prometedora para mejorar las características del bio-oil.Palabras clave: Hidrotalcitas, ciclopentanol, furfuril alcohol, cobre, mejora del bio-aceite.

Constructing Ni–Pt Bimetallic Catalysts for Catalytic Hydrogenation and Rearrangement of Furfural into Cyclopentanone with Insight in H/D Exchange by D2O Labeling

“…2-Cyclopentenone (CPEO) is generated via dehydration. Finally, the hydrogenation of CPEO generates CPO under a H 2 or D 2 atmosphere. − The generated CPO in D 2 O shows an increased mass/charge ratio ( m / z ) than that in water, confirming the transfer of D atoms from D 2 O to intermediates and products during hydrogenation and rearrangement processes. This investigation confirms that water is a reactive solvent for the rearrangement process and a hydrogen source for the reaction.…”

Aqueous phase hydrogenation of furfural on Ni/TiO2 catalysts: nature of the support phase steers the product selectivity

“…The protonated intermediate formation in aqueous phase and the subsequent transformations are catalysed by acidic sites. 48,49 However, the nickel catalysts supported on pure anatase titania have resulted in only the formation of CPO, whereas on mixed phase and rutile catalysts, additional deep hydrogenated products such as CPOL and THFOL are also formed. With the exception of the RTS catalyst, FOL is completely consumed in reaction over other mixed and rutile samples with a remarkable conversion of 100%.…”

An overview of catalysts for the hydrodeoxygenation reaction of model compounds from lignocellulosic biomass

“…These supports have been used in various types of reactions with biomass-derived model molecules, such as hydration reactions, aldol condensation, isomerization, among which HDO reactions have also been studied. Pino et al [136] used Cu catalysts supported on Mg and Al hydroxide hydrotalcites for the HDO reaction of furfuryl alcohol (200 • C and 50 bar). It was reported that the catalyst activity was dependent on the Mg 2+/ Al 3+ ratio, although most of the products obtained are oxygenated intermediates, not reaching complete deoxygenation of the furfuryl alcohol.…”

“…Pino et al. [136] used Cu catalysts supported on Mg and Al hydroxide hydrotalcites for the HDO reaction of furfuryl alcohol (200°C and 50 bar). It was reported that the catalyst activity was dependent on the Mg 2+/ Al 3+ ratio, although most of the products obtained are oxygenated intermediates, not reaching complete deoxygenation of the furfuryl alcohol.…”