Glycerol as a raw material to the biorrefinery

COMELLI, RAÚL A.

Sitges

Conferencia; 1st International Conference BIORESOURCE TECHNOLOGY for Bioenergy, Bioproducts & Environmental Sustainability; 2016

BIORESTEX

Glycerol, the co-product in biodiesel process, can be fed as raw material to a biorefinery. Reactions of selective oxidation and reduction, steam reforming, and hydrogenolysis of glycerol were studied to produce added-value chemicals and energetic compounds, and also to show the possible integration of processes in a framework of biorefinery; projects actually in development to scaling up some processes were also mentioned. The following materials were prepared: i) Potassium ferrierite impregnated with Pt (2.5-7.5wt.%) and Bi (5-10wt.%), identified as Pt/K-Fer; ii) alumina impregnated with Cu (2-40 wt.%) with and without Ce (2-29wt.%), identified as Cu-Ce/Al2O3; iii) alumina impregnated with Ni (2.6-9.9 wt.%) modified with Ce, Co, Mg, or Zr, identified as Ni-(Ce-Co-Mg-Zr)/ Al2O3; ammonium and potassium ferrierite impregnated with Ru (1-5wt.%). Catalysts were characterized by N2 adsorption, temperature-programmed reduction, ammonia temperature-programmed desorption, FTIR, and X-ray diffraction. The selective oxidation of glycerol to dihydroxyacetone (DHA) took place on Pt/K-FER, improving its performance by adding Bi, reaching Pt-Bi/K-FER 75.9 and 93.9% of glycerol conversion and DHA selectivity, respectively. The selective reduction of glycerol to propyleneglycol (PG) in gas phase was studied using Cu containing catalysts, reaching the best performance Cu-Ce/Al2O3 with 99.8 and 83.2% of glycerol conversion and selectivity to PG, respectively. This last reaction demands hydrogen, which can be obtained by steam reforming of glycerol; the performance of Ni/Al2O3, being the performance modified by adding other compounds such as Ce, Co, Mg, and Zr; the steam reforming also produces carbon oxides and methane, being possible to use syngas and methane as energetic compounds and carbon dioxide to carbonylation of glycerol. Preliminary results with Ru/H-FER showed that preparation technique of catalysts is important to obtain active material to convert glycerol to methanol; 3wt.% Ru added in three steps produced methanol when preparation included calcining treatment between each impregnating step but methanol was not formed when intermediate calcining treatments did not take place. Consequently, feeding only glycerol and integrating processes it is possible to obtain DHA, PG, acetol, hydrogen, syngas, carbon dioxide, methane, and methanol.