The GLYCEROL AS RAW MATERIAL TO AN ARGENTINIAN BIOREFINERY

LISANDRO FERRARI; FERNANDO TULER; EZEQUIEL PROMANCIO; LEONARDO GUSE; DIEGO GARCÍA TOUZA; CARLOS CASAS; RAÚL COMELLI

Congreso; 11th World Congress of Chemical Engineering; 2023

Glycerol, the “co-product” in the biodiesel process, can be fed as a raw material to biorefinery. Selective oxidations and reductions and steam reforming of glycerol were studied to produce added-value chemicals and energetic compounds, and also to show a possible integration of processes into a biorefinery framework. Selective oxidations of glycerol in liquid phase produced: i) dihydroxyacetone on Pt/K-FER, being the first active and selective monometalliccatalyst in this transformation, improving the catalytic behavior by using Pt-Bi/K-FER, reaching 75.9% conversion and 93.9% selectivity to dihydroxyacetone; and ii) lactic acid on Cu/Al2O3, obtaining 99.8% conversion and 86.5% selectivity to lactic acid. Selective reductions of glycerol in gas phase produced: i) propylene glycol on Cu-Ce/Al2O3, reaching 99.8% conversion and 83.2% selectivity to propylene glycol [1]; and ii) ethylene glycol on Ni/SiO2, achieving 100% conversion and 91% selectivity to ethylene glycol in the liquid fraction. These reduction reactions demand hydrogen, which can be obtained by steam reforming of glycerol using Ni/Al2O3 promoted by adding compounds as Ce, Co, Mg, and Zr; the steam reforming also produced carbon oxides and methane, being possible to use the syngas (hydrogen plus carbon monoxide) and methane as energetic compounds and carbon dioxide to carbonylation. From the strong link with the productive sector, two pilot plants are in the final building step, one to produce 100 tn/y of propylene glycol from glycerol but versatile to also obtain acetol and/or ethylene glycol, and another one for reforming glycerol to produce the hydrogen demanded for those reduction processes. Consequently, glycerol was converted to dihydroxyacetone, lactic acid, propylene glycol, ethylene glycol, hydrogen, syngas, carbon dioxide, and methane; then, the possible integration of the corresponding processes allow to consider the co-product of biodiesel as an example to apply the concept biorefinery [2]. In 2021, the work "GLYCEROL as Raw Material for BIOREFINERY" received the Technological Innovation Award from the ACADEMIA NACIONAL de CIENCIAS EXACTAS, FÍSICAS y NATURALES – ANCEFN. Nowadays, a new project is starting being its objective to design and build an integratedplatform to validate in a bench scale, catalytic processes which taking place in both liquid and gas phase, adding value to the oleochemical chain, using initially glycerol as raw material.