Selective production of guaiacol from lignin via catalytic transfer hydrogenolysis using Ru-Cu/Zirconia

Abstract

In this study, the effect of calcination temperature of zirconia support (400, 600, and 800 °C) and the role of bimetallic Ru-Cu over monometallic (Cu, Ru) catalysts are evaluated for catalytic transfer hydrogenolysis of alkali lignin. The prepared catalysts were characterized extensively for crystallinity, pore size distribution, acidity, thermal stability and chemical oxidation state. The transformation of zirconia from non-crystalline to crystalline phase was observed with increasing calcination temperature. The pores transformed from wide ink bottle shape into cylindrical shape with increased calcination temperature. The XPS analysis revealed the existence of Cu0 (60%) in presence of Ru with a concomitant reduction in Ru4+ on the surface of the catalyst, which is attributed to increased crystallinity of zirconia in the presence of copper. High yields of total monomers (32.4 wt.%) and guaiacol (12.7 wt.%) were obtained under the optimized condition (270 °C, 3 h) with Ru-Cu/ZrO2 when ZrO2 was calcined at 800 °C. The mesoporous nature of zirconia and the strong metal-support interaction exhibited by Ru-Cu are shown to influence the formation of monomers. Increase in temperature from 225 to 270 °C enhanced the yield of guaiacol, 4-methyl guaiacol and 4-ethyl guaiacol with a concomitant reduction in the yield of trans-isoeugenol, demonstrating the cleavage of C–C bonds. The recyclability tests of the catalyst showed that the yield of guaiacol remained stable even after two cycles of catalyst reuse without calcination.