Scaling of sustainable technologies to transform glycerol into added-value and energetic compounds

COMELLI, RAÚL A.; FERRARI, LISANDRO; TULER, FERNANDO; CASAS, CARLOS; GARCÍA TOUZA, DIEGO

Illinois

Simposio; 2021 American Oil Chemists' Society (AOCS) - Annual Meeting & Expo - Section: Industrial Oil Products. New Uses of Glycerine; 2021

American Oil Chemists' Society - AOCS

Glycerol, the co-product in biodiesel production, is intermediary for synthesis of a large number of compounds for industry. In Argentina, in the Province of Santa Fe, a capacity of 4.0 Mtons annual of biodiesel is installed, being available 400,000 tons/year of glycerol. The problem of its increasing availability is not resolved adopting a monoproduct strategy, because this one would become the new problem; consequently, solution must have a diversification approach and the concept of Biorefinery can be applied. Since 2007, catalytic processes have been developed to convert glycerol into industrially applicable compounds with high added-value, such as dihydroxyacetone (DHA), acetol, propylene glycol (PG), ethylene glycol (EG), 1,3-propanediol, lactic acid, and methanol, as well as compounds with energetic use such as hydrogen, syngas, and ethers of glycerol. Reactions of selective oxidation and reduction, hydrogenolysis, and steam reforming were studied, showing the possible integration of processes in a biorefinery environment; DHA, acetol, PG, EG, lactic acid, hydrogen, syngas, carbon dioxide, methane, and methanol can be obtained feeding only glycerol. Three catalysts and processes were developed and patented: i) selective oxidation to DHA on Pt-Bi/K-FER, reaching 75.9% glycerol conversion and 93.9% selectivity to DHA; ii) selective reduction to PG in gas phase on Cu-containing catalysts, reaching the best performance Cu-Ce/Alumina, with 99.8% glycerol conversion and 83.2% and 14.3% selectivities to PG and acetol (the reaction intermediate), respectively; and iii) hydrogenolysis to EG on Ni/SiO2, obtaining 100% glycerol conversion and 91.0% selectivity to EG in the liquid fraction. Finally, from a strong link with the productive sector, financing was obtained to build two pilot plants, one to produce 100 tn/year of PG but versatile to also produce acetol and/or EG, and another one for reforming glycerol to obtain hydrogen, which is raw material for selective reductions; both plants would be in operation during 2021.