Selective conversion of cellulose to hexitols over bi-functional Ru-supported sulfated zirconia and silica-zirconia catalysts

Abstract

We report a process of selective conversion of microcrystalline cellulose to hexitols over bi-functional Ru-supported sulfated zirconia and silica-zirconia catalysts. A 58.1% yield of hexitols and a 71.0% conversion of cellulose were achieved over Ru/SZSi(100:15)-773 catalyst at 443 K. The as-synthesized catalysts were characterized by X-ray diffraction (XRD), BET, thermogravimetric analysis and pyridine adsorption Fourier transform infrared spectroscopy (FTIR). XRD results indicated that the sulfated catalysts were pure tetragonal phase of ZrO₂ when calcined at 773 K. Monoclinic zirconia appeared at the calcination temperature of 873 K, and the content of monoclinic phase increased with the elevating temperature. Compared with sulfated zirconia catalyst, sulfated silica-zirconia catalysts possessed a higher ratio of Brønsted to Lewis on the surface of catalysts, as shown from pyridine adsorption FTIR results. The reaction results indicated that the tetragonal zirconia, which is necessary for the formation of superacidity, was the active phase to cellulose conversion. The higher amounts of Brønsted acid sites can remarkably accelerate the cellulose depolymerization and promote side reactions that convert C5–C6 alcohols into the unknown soluble degradation products.

Graphical abstract

Keywords

cellulose / hexitols / hydrogenation / sulfated zirconia / ruthenium

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Acknowledgments

The work was supported by National Natural Sciences Foundation of China (Grant Nos. 21076152 and 21276191). Special Research Fund for the Doctoral Program of Higher Education of China (Grant No. 2100032110018), and the Program of Introducing Talents of Discipline to Universities, China (Grant No. B06006). The authors would like to thank Dr. Li Fang for the in situ FTIR of pyridine adsorption measurement.

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2014 Higher Education Press and Springer-Verlag Berlin Heidelberg