Group of Sustainable Energy and Chemistry, Institute of Catalysis and Petrochemistry (CSIC), C/Marie Curie 2, 28049 Madrid, Spain.
ChemSusChem. 2012 Oct;5(10):1984-90. doi: 10.1002/cssc.201200167. Epub 2012 Jul 30.
Furfural can be converted into maleic anhydride (73 % yield) through selective gas phase oxidation at 593 K with O(2) by using VO(x)/Al(2)O(3) (10 at(V) nm(-2)) as solid catalysts. The use of lower temperatures and/or O(2) pressures result in the additional formation of furan (maximum 9 % yield). Mechanistically, furfural (C(5)H(4)O(2)) is oxidized stepwise to furan (C(4)H(4)O), 2-furanone (C(4)H(4)O(2)), and finally, maleic anhydride (C(4)H(2)O(3)). The specific structure of the supported vanadium oxides and reaction conditions (temperature and reactants pressures) all influence furfural oxidation catalysis. We have found that Al(2)O(3)-supported polyvanadates are intrinsically more active (2.70 mmol h(-1) g-at V(-1)) than monovanadates (VO(4)) and V(2)O(5) crystals (0.89 and 0.70 mmol h(-1) g-at V(-1), respectively) in maleic anhydride and furan formation rates (553 K, 1.6 kPa furfural, 2.5 kPa O(2)). Our alternative approach enables the use of biomass instead of petroleum to synthesize maleic anhydride and furan from furfural. The potential variety of industrial applications is of enormous interest for the development of future biorefineries.
糠醛可以在 593K 下用 O(2)进行选择性气相氧化,转化为马来酸酐(产率 73%),使用 VO(x)/Al(2)O(3)(10 at(V) nm(-2)) 作为固体催化剂。使用较低的温度和/或 O(2)压力会导致呋喃(最大产率 9%)的额外形成。从机理上讲,糠醛(C(5)H(4)O(2)) 逐步氧化为呋喃(C(4)H(4)O)、2-呋喃酮(C(4)H(4)O(2)),最后转化为马来酸酐(C(4)H(2)O(3))。负载型钒氧化物的具体结构和反应条件(温度和反应物压力)都影响糠醛氧化催化。我们发现,氧化铝负载的多钒酸盐比单钒酸盐(VO(4)) 和 V(2)O(5) 晶体(分别为 0.89 和 0.70 mmol h(-1) g-at V(-1)) 内在活性更高,在马来酸酐和呋喃的形成速率(553K、1.6kPa 糠醛、2.5kPa O(2)) 中。我们的替代方法可以利用生物质代替石油,从糠醛合成马来酸酐和呋喃。未来生物精炼厂的发展对工业应用的潜在多样性具有极大的兴趣。