Etherification of 5-hydroxymethyl-2-furfural (HMF) with ethanol to biodiesel components using mesoporous solid acidic catalysts

• Published in: Catalysis today Vol. 175; no. 1; pp. 435 - 441
• Main Authors: Lanzafame, P., Temi, D.M., Perathoner, S., Centi, G., Macario, A., Aloise, A., Giordano, G.
• Format: Journal Article Conference Proceeding
• Language: English
• Published: Amsterdam Elsevier B.V 25.10.2011; Elsevier
• Subjects: Acid sites; acidity; biodiesel; Biodiesel components; bioethanol; Catalysis; catalysts; catalytic activity; Chemistry; Colloidal state and disperse state; ethane; Ethanol; Etherification; Exact sciences and technology; General and physical chemistry; HMF; hydrogenation; hydroxymethylfurfural; Mesoporous catalysts; Porous materials; silica; Theory of reactions, general kinetics. Catalysis. Nomenclature, chemical documentation, computer chemistry; HMF; Acid sites; Ethanol; Mesoporous catalysts; Etherification; Biodiesel components; Furan; Furfural; Strong acidity; Support; Acidic site; Alcohol; Selectivity; Porous material; Silica; Solid; Brönsted acid; Zirconium oxide; Alkanol; Defect; Ion exchange resin; Lewis acid; Lewis site; Reaction product; Transition element compounds; Strong acid; Bronsted site; Ethane; Mesoporosity; Zirconia; Heterogeneous catalysis; Catalyst; Environmental protection
• ISSN: 0920-5861; 1873-4308
• DOI: 10.1016/j.cattod.2011.05.008

[Display omitted] ► Selective etherification of HMF with ethanol to biodiesel components. ► Formation of 5-(ethoxymethyl)furan-2-carbaldehyde (EMF), 1,1-dietoxy ethane (DE) and ethyl 4-oxopentanoate (EOP). ► The selectivity to EMF and EOP is closely related to the presence of Lewis and/or Brønsted acidity on the catalyst. ► Selective EOP synthesis in a one-step, which can be hydrogenated to valeric biofuels. The etherification of 5-hydroxymethyl-2-furfural (HMF) with ethanol is studied over a series of mesoporous silica catalysts (Al-MCM-41 materials with different Si/Al ratio, and zirconia or sulfated zirconia supported over SBA-15) and compared with the behavior of H 2SO 4 and Amberlyst ®15. The observed reaction products were 5-(ethoxymethyl)furan-2-carbaldehyde (EMF), 1,1-dietoxy ethane (DE) and ethyl 4-oxopentanoate (EOP). The selectivity to EMF and EOP is closely related to the presence of Lewis and/or Brønsted acidity on the catalyst, while the formation of DE is probably related to defect sites. The latter, being less reactive, catalyze the side reaction to DE only when strong Lewis and/or Brønsted acid sites are absent. Catalysts with only a strong Brønsted acidity react selectively to form EOP. When strong Lewis acid sites are present in the catalyst, e.g. by introducing ZrO 2 in SBA-15 or when extra-framework isolated Al 3+ sites are present in the mesoporous channels, a high selectivity to EMF was observed. The results indicate that EMF, DE or EOP can be obtained selectively by direct reaction of HMF with bioethanol by tuning the acidity of the catalyst. EMF is a value biodiesel component, but the results also evidence the possibility to obtain selectively EOP in a one-step reaction, opening interesting perspectives to produce valeric biofuels by subsequent selective hydrogenation.