Catalytic dehydration of d-xylose to 2-furfuraldehyde in the presence of Zr-(W,Al) mixed oxides. Tracing by-products using two-dimensional gas chromatography-time-of-flight mass spectrometry

Zirconium-tungsten mixed oxides (ZrW) are effective catalysts in the aqueous-phase dehydration of d-xylose to 2-furfuraldehyde (Fur), at 170 °C. The texture and acid properties of ZrW materials were modified to enhance Fur yields. The catalysts prepared by co-condensation without a templating agent (ZrW(X), X = NO3, Cl; X is related to the type of zirconium precursor) possess relatively low specific surface area and amounts of accessible acid sites, leading to a modest Fur yield of ca. 35% at 99% conversion. The use of a templating agent in the preparation of mesoporous ZrW (ZrW-MP) increased considerably the specific surface area and the amount of accessible acid sites, which resulted in enhanced Fur yields (42%) reached at comparable conversions. Further improvements in Fur yields at high conversions were accomplished by introducing aluminium in the catalyst preparation procedure to give ZrAlW-MP (51% yield at 98% conversion). Fairly good catalytic results were also obtained in the case of the ZrAlW-MP catalyst, using solely water as solvent (46% yield at 93% conversion). A study of the identification of the reaction by-products by two-dimensional gas chromatography (GC × GC) combined with time-of-flight mass spectrometry (ToFMS) was carried out.

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► Zr–W mixed oxides are solid acid catalysts in the aqueous phase dehydration of xylose into furfural.
► The texture and acid properties of Zr–W mixed oxides can be modified to enhance furfural yields.
► Catalyst preparation using a surfactant template and doping with Al enhances surface area and acidity.
► Identification of the water-soluble reaction by-products by SPME/GC × GC–ToFMS analyses.