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Biodiesel Glycerin Valorization into Oxygenated Fuel Additives

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Abstract

Current industrial methods of biodiesel production lead to an excess of crude glycerin which requires costly purification before commercialization. Production of oxygenated fuel additives is a potential route for glycerin valorization. Glycerin acetylation was carried out over heterogeneous acid catalysts (15%, glycerol weight basis) using glacial acetic acid (molar ratio = 9). The catalysts, containing different amounts of phosphate species (P/Si from 10 to 20 atomic ratio), were prepared by wet impregnation of commercial silica with aqueous solutions of diammonium phosphate and ortho-phosphoric acid. X-ray diffraction patterns of calcined solids presented amorphous patterns like raw silica. The prepared catalysts presented, at 120 °C, glycerol conversion higher than 89.5% after 1 h of reaction, been diacetin the major product, with triacetin selectivities lower than 26.1%. Diacetin selectivity was found to be almost invariant with catalyst acidity thus underlining the relevance of catalyst porosity due to the large acetins molecules sizes. The slow rate of triacetin diffusion in narrow pores of catalyst might be responsible for the relatively low yield obtained. Surface phosphate species showed a slow rate of leaching in the reaction medium showing high catalyst stability.

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Acknowledgements

The team would like to acknowledge Raisa Paes Santiago and André Aguilar for all the help given during glycerin acetylation tests and acknowledge FCT (Fundacão para a Ciência e Tecnologia, Portugal) for funding project PTDC/EMS-ENE/4865/2014. The author F. G. Fonseca is a member of the Bioeconomy Graduate Program BBW ForWerts.

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Authors and Affiliations

  1. IDMEC, CERENA, Instituto Superior Técnico, Universidade de Lisboa, Av. Rovisco Pais, 1, 1049-001, Lisbon, Portugal

    Ana Paula Soares Dias, Mónica Catarino & João Gomes

  2. Institute of Catalysis Research and Technology (IKFT), Karlsruhe Institute of Technology (KIT), 76344, Eggenstein-Leopoldshaven, Germany

    Frederico Gomes Fonseca

  3. ADEQ, Instituto Superior de Engenharia de Lisboa, Instituto Politécnico de Lisboa, R. Conselheiro Emídio Navarro, 1, 1959-007, Lisbon, Portugal

    João Gomes

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  1. Ana Paula Soares Dias
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  2. Frederico Gomes Fonseca
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  3. Mónica Catarino
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APSD Conceptualization, Resources, Supervision, Funding acquisition, Writing-Reviewing and editing. FGF Investigation, Formal Analysis, Writing Original Draft, Reviewing and Editing. MC Investigation, Writing Original Draft. JG Writing, Reviewing and Editing.

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Correspondence to Ana Paula Soares Dias.

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Soares Dias, A.P., Gomes Fonseca, F., Catarino, M. et al. Biodiesel Glycerin Valorization into Oxygenated Fuel Additives. Catal Lett 152, 513–522 (2022). https://doi.org/10.1007/s10562-021-03646-0

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