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Sustentabilidad DEL Biodiesel Utilizando EL Glicerol Como Materia PRIMA PARA BiorefinerÍa

Sustentabilidad DEL Biodiesel Utilizando EL Glicerol Como Materia PRIMA PARA BiorefinerÍa

Authors: 
Comelli, R. A. - Presenter, INCAPE (FIQ-UNL, CONICET)
The process to produce biodiesel generates glycerol as by-product, interesting its transformation into added-values compounds and/or energetic ones to improve the sustainability of the overall process. In the province of Santa Fe, in the influencing area of Greater Rosario, a capacity of 2.5 million tons annual of biodiesel is installed, generating consequently 250,000 tons/year of glycerol. Glycerol is an intermediate to synthesis of large amount of compounds employed to industries, but the problem related to its increasing availability linked to the increased production of biodiesel is not solved by adopting a single-product strategy, because it would become the new problem; consequently, solution should have a diversified approach such as applying the concept of biorefinery, which is the functional unit that converts biomass into added-value products and other ones capable to supply energy. In this context, catalytic processes were developed to transform sustainability glycerol to compounds with industrial applications, such as dihydroxyacetone (DHA), acetol, propyleneglycol (PG), 1,3-propanediol, lactic acid, and methanol, as well as compounds with energetic use such as hydrogen, synthesis gas, and ethers of glycerol. Reactions of selective oxidation and reduction, steam reforming, and hydrogenolysis of glycerol were studied, showing the possible integration of processes in an environment of biorefinery. Selective oxidation to DHA occurred on Pt/K-FER, improving with Pt-Bi/K-FER, reaching 75.9% conversion and 93.9% selectivity to DHA. Selective reduction to PG in gas phase took place on Cu-containing catalysts, reaching the best performance Cu-Ce/Alumina, with 99.8% conversion and 83.2% selectivity to PG, being the main byproduct acetol (14.3%), which is the reaction intermediate. Oxidation to lactic acid, which demand is increasing, occurred on Cu/Alumina with Cu loadings between 6 and 40%w/w, at 240ºC and 1.4 MPa, reaching the best performance the material with the largest loading. The steam reforming produced mainly hydrogen, carbon oxides, and methane, depending of the catalyst design and operating conditions that favor either the formation of hydrogen, an energy vector considered the future fuel, or the production of synthesis gas, a mixture of hydrogen and carbon monoxide, which can be used for methanol and Fisher-Tropsch synthesis or as a fuel mixture; catalysts of nickel supported on alumina, modified with Zr, Mg, Ce, and Co, were prepared, characterized, and evaluated. Moreover, the hydrogenolysis of glycerol in liquid phase to methanol, which is raw material for biodiesel production, allowing it the biodiesel process as a fully sustainable one; Ru-containing catalysts showed promising results. Consequently, only feeding glycerol and integrating processes is possible to obtain DHA, PG, acetol, lactic acid, hydrogen, synthesis gas, carbon dioxide, methane, and methanol. Two catalysts, for selective oxidation to DHA and selective reduction to PG, were developed and patented; moreover, a funding to scaling up a pilot plant to produce 100 tn of PG per year was obtained, while another funding was solicited for scaling up the steam reforming process to a pilot plant to produce hydrogen, which is raw material into the selective reduction.