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

doi:10.1007/s11705-015-1543-1

Front. Chem. Sci. Eng.

2015, Vol. 9

Issue (4) : 461-466 https://doi.org/10.1007/s11705-015-1543-1

RESEARCH ARTICLE

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

Zhiqiang Song,Hua Wang,Yufei Niu,Xiao Liu,Jinyu Han(

)

Key Laboratory for Green Chemical Technology, School of Chemical Engineering and Technology, Tianjin University; Collaborative Innovation Center of Chemical Science and Engineering, Tianjin 300072, China

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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.

Keywords hexitols cellulose hydrogenation sulfated zirconia ruthenium

Corresponding Author(s): Jinyu Han

Online First Date: 18 November 2015 Issue Date: 26 November 2015

Cite this article:

Hua Wang,Yufei Niu,Xiao Liu, et al. Selective conversion of cellulose to hexitols over bi-functional Ru-supported sulfated zirconia and silica-zirconia catalysts[J]. Front. Chem. Sci. Eng., 2015, 9(4): 461-466.

URL:

https://academic.hep.com.cn/fcse/EN/10.1007/s11705-015-1543-1
https://academic.hep.com.cn/fcse/EN/Y2015/V9/I4/461

Fig.1 XRD patterns of catalysts. (A) Ru/Z-773; (B) Ru/SZ- 773; (C) Ru/SZ-873; (D) Ru/SZ-973; (E) Ru/SZSi(100:15)-773; (F) Ru/SZSi(100:100)-773

Tab.1 Physicochemical characteristics of catalysts

Fig.2 N₂ adsorption-desorption isotherms of sulfated zirconia and silica-zirconia catalysts

Fig.3 FTIR spectra of catalysts. (A) Ru/SZ-773; (B) Ru/SZSi (100:15)-773; (C) Ru/SZSi(100:100)-773

Fig.4 TGA and DTG curves of catalysts. (A) TGA curve of Ru/SZ-773; (B) TGA curve of Ru/SZSi(100:15)-773; (C) DTG curve of Ru/SZ-773; (D) DTG curve of Ru/SZSi(100:15)-773

Tab.2 Catalytic performance for hydrogenation of cellulose^a)

Fig.5 Reusability of Ru/SZ-773 and Ru/SZSi (100:15)-773 catalysts

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