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Biomass Valorization

The field of chemistry and related industries are undergoing a profound change due to strategic transformation from fossil to renewable feedstock. One of the most important issues is the exploitation of local natural resources to produce chemicals, polymers and other high added-value products. The bio-based chemical industry can be sustainable if implemented in an integrated approach considering environmental issues related to availability of resources. However, these products are in most cases polyfunctional and their transformations require the close control of the chemio- and/or regio- and/or enantioselectivity of processes. To overcome these problems, catalysis is expected to play a pivotal role by offering useful tools for the upgrading of products derived from bio-resources to higher value chemicals. Fine chemicals from renewable is an area in which various examples already exist, demonstrating that natural products play an important role in chemical production.

Our group studies the design and synthesis of highly selective solid catalysts for the valorization of bio-resources. The cooperative behaviour of surface sites with metallic, acidic, basic, or reduction-oxidation properties is an essential requirement for catalysis, and the design of such complex catalytic materials is at the forefront of academic and industrial research. Current research lines in our group includes the valorization of polyols , lactic acid, and sugars by obtaining valuable chemicals, and the synthesis of γ-butyrolactone from succinic acid and maleic anhydride.

Reactions   

  • Valorization of glycerol
    The synthesis of a platform compound such as 3-hydroxyppropionic acid (3-HP) is studied taking advantage of an abundant renewable resource in Argentina and in Santa Fe region. This resource is glycerol, which is obtained as by-product during biodiesel synthesis. Indeed, the use of triglycerides of soybean oil, abundant in our country and especially in our Litoral region, for the production of biodiesel by methanolysis reactions generates an abundant amount of glycerol as a by-product. The transformation of glycerol through consecutive dehydration-H transfer reactions-oxidation to obtain the desired platform compound, 3-hydroxypropionic acid, is investigated in both gas and liquid phases. The 2-propen-1-ol (allylic alcohol) is obtained as reaction intermediate. The synthesis requires the development of solid bifunctional metal/acid catalysts. The acid sites are required to promote the dehydration reaction and the metal ones to allow the oxidation reaction in oxidizing atmosphere. In addition, it is sought to valorize the 3-HP acid by transforming it into acrylic acid (AA). The synthesis of AA is carried out in liquid phase, in a batch reactor and involves a dehydration reaction that requires the use of acid solids as catalysts.      

  • Valorization of polyols
    We study the valorization of polyols, such as 1,3-butanediol and 1,4-butanediol, via dehydration and dehydrogenation reactions. Specifically, we investigate the gas-phase production of valuable alcohols, aldehydes, ketones and hydroxyketones which are widely used as additives and intermediate compounds in organic synthesis. Design and development of efficient solid catalysts allows the selective promotion of the desired chemical product.      

  •  Valorization of sugars 
    Sugars produced in biorefineries by polysaccharide hydrolysis may be converted to valuable polyfunctional chemicals of industrial interest. Our group study the synthesis of butanediols from C4 and C5 sugars via decarbonylation and hydrogenolysis reactions. Butanediols are currently obtained from oil-derived compounds and are widely employed to produce valuable polyesters, resins and plasticizers. We also study in our group the synthesis of ethyl lactate (EL) and pyruvic aldehyde ethyl lactate (PADA) from triose sugars such as dihydroxyacetone. EL is used as green solvent, plasticizer, and in pharmaceutical and cosmetic formulations, while PADA is employed in the synthesis of folic acid. 

  •  Synthesis ofγ-butyrolactone from succinic acid and maleic anhydride:
    Succinic acid is a versatile compound that is produced through the fermentation of glucose. By successive dehydrogenation/dehydration reactions, succinic acid is converted to maleic anhydride which in turns may form γ-butyrolactone by hydrogenation/hydrogenolysis pathways. γ-Butyrolactone is a selective and specific solvent that may replace current environmentally aggressive chloride solvents, and is also a valuable intermediate used in polymer, agrochemical and pharmaceutical industries. Our group studies the one-step synthesis of γ-butyrolactone from maleic anhydride by using non-noble metals (Ni, Cu, Co, Fe) supported on different acid mixed oxides of meso- and micropore structure.

  •  Valorization of lactic acid
    Lactic acid is commercially produced through the fermentation of glucose. It is extremely reactive as it contains both hydroxyl and carboxy functional groups and may accordingly undergo a variety of reactions leading to valuable chemicals. The aim of our studies is the development of selective acid catalysts for producing acrylic acid from lactic acid dehydration or acetaldehyde by decarbonylation. This is an attractive target for new bio-based compounds because acrylic acid and acetaldehyde are totally obtained today from fossil raw materials, mainly via direct oxidation of propene and ethylene.

    Recent Publications

    • Kinetic analysis of the conversion of aqueous erythritol solution on Ir/ReOx/TiO2 in a batch slurry reactor, Emanuel M. Virgilio, María E. Sad, Cristina L. Padró, Applied Catalysis A: Gen 643 (2022) 118691.
    • Effect of support properties on selective butanediols production from erythritol using Ir/ReOx catalysts, E.M. Virgilio, C.L. Padró, M.E. Sad, ChemCatChem, 13(17), 3889-3906 (2021).
    • Study of catalyst deactivation during 1,3-butanediol dehydration to produce butadiene A.C. Rodriguez, M.E. Sad, H. Cruchade, L. Pinard, C.L. Padró, Microporous Mesoporous Mater., 320,111066 (2021).
    • Butanediols production from erythritol on Rh promoted catalyst, E.M. Virgilio, C.L. Padró, M.E. Sad, Latinam. Appl. Res., 50(2), 89-94 (2020).
    • Kinetic and mechanistic study of triose sugar conversion on Lewis and Brønsted acid solids, E.A. Pighin, J.I. Di Cosimo, V.K. Díez, Molec. Catal., 458, 189-197 (2018).
    • Selective synthesis of acetaldehyde from lactic acid on acid zeolites, M.E. Sad, L.F. González Peña, C.L. Padró, C.R. Apesteguía, Catal. Today 2, 203-209 (2018).
    • Kinetic study of the ethyl lactate synthesis from triose sugars on Sn/Al2O3 catalysts, E. Pighin, V.K. Díez, J.I. Di Cosimo, Catal. Today, 289, 29-37 (2017).
    • Highly selective Cu-modified Ni/SiO2-Al2O3 catalysts for the conversion of maleic anhydride to γ-butyrolactone in gas phase, M.E. Bertone, S.A. Regenhardt, C.I. Meyer, V. Sebastian, T.F. Garetto, A.J. Marchi, Topic. Catal., 59, 159-167 (2016).
    • Synthesis of ethyl lactate from triose sugars on Sn/Al2O3 catalysts, E. Pighin, V.K. Díez, J.I. Di Cosimo, Appl. Catal. A: General, 517, 151-1605 (2016).
    • Highly selective conversion of maleic anhydride to γ-butyrolactone over Ni-supported catalysts prepared by precipitation–deposition method, M.E. Bertone, C.I. Meyer, S.A. Regenhardt, V. Sebastian, T.F. Garetto, A.J. Marchi, Appl. Catal. A: General, 503, 135-146 (2015).
    • Upgrading of diols by gas-phase dehydrogenation and dehydration reactions on bifunctional Cu-based oxides, P.A. Torresi, V.K. Díez, P.J. Luggren, J.I. Di Cosimo, Catal. Sci. Technol., 4, 3203-3213 (2014).
    • Gas-phase conversion of 1,3-butanediol on single acid-base and Cu-promoted oxides V.K. Diez, P.A. Torresi, P.J. Luggren, C.A. Ferretti, J.I. Di Cosimo, Catal. Today, 213, 18-24 (2013).

    • Gas-phase maleic anhydride hydrogenation over Ni/SiO2-Al2O3 catalysts: Effect of metal loading, C.I. Meyer, S.A. Regenhardt, M.E. Bertone, A.J. Marchi, T.F. Garetto, Catal. Lett., 143, 1067-1073 (2013).

    • Conversion of diols by dehydrogenation and dehydration reactions on silica-supported copper catalysts, P.A. Torresi, V.K. Diez, P.J. Luggren, J.I. Di Cosimo, Appl. Catal. A: General, 458, 119-129 (2013).

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