1. Characterization of copper-containing porphyrins in an insoluble fraction of a bio-crude obtained from hydrothermal liquefaction of wild microalgae
- Author
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Maillard, J.F. (Julien F.), Mase, C. (Charlotte), Serve, O. (Olivier), Vezin, H. (Hervé), Afonso, C. (Carlos), Giusti, P. (Pierre), Mangote, C. (Caroline), Université de Rouen Normandie (UNIROUEN), Normandie Université (NU), International Joint Laboratory - Complex Matrices Molecular Characterization (iC2MC), Normandie Université (NU)-Normandie Université (NU)-Université de Pau et des Pays de l'Adour (UPPA)-Centre National de la Recherche Scientifique (CNRS)-Total Energies, Chimie Organique et Bioorganique : Réactivité et Analyse (COBRA), Institut de Chimie Organique Fine (IRCOF), Normandie Université (NU)-Normandie Université (NU)-Institut national des sciences appliquées Rouen Normandie (INSA Rouen Normandie), Institut National des Sciences Appliquées (INSA)-Normandie Université (NU)-Institut National des Sciences Appliquées (INSA)-Centre National de la Recherche Scientifique (CNRS)-Université de Rouen Normandie (UNIROUEN), Institut National des Sciences Appliquées (INSA)-Normandie Université (NU)-Institut National des Sciences Appliquées (INSA)-Centre National de la Recherche Scientifique (CNRS)-Institut Normand de Chimie Moléculaire Médicinale et Macromoléculaire (INC3M), Université de Caen Normandie (UNICAEN), Normandie Université (NU)-Normandie Université (NU)-École Nationale Supérieure d'Ingénieurs de Caen (ENSICAEN), Normandie Université (NU)-Université Le Havre Normandie (ULH), Normandie Université (NU)-Université de Rouen Normandie (UNIROUEN), Normandie Université (NU)-Institut national des sciences appliquées Rouen Normandie (INSA Rouen Normandie), Institut National des Sciences Appliquées (INSA)-Normandie Université (NU)-Institut National des Sciences Appliquées (INSA)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS)-Université de Caen Normandie (UNICAEN), Normandie Université (NU)-École Nationale Supérieure d'Ingénieurs de Caen (ENSICAEN), Normandie Université (NU)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS)-Centre National de la Recherche Scientifique (CNRS), TotalEnergies, Total Energies, Laboratoire Avancé de Spectroscopie pour les Intéractions la Réactivité et l'Environnement - UMR 8516 (LASIRE), Institut de Chimie du CNRS (INC)-Université de Lille-Centre National de la Recherche Scientifique (CNRS), TOTAL Research & Technology Gonfreville (TRTG), Université de Lille, CNRS, International Joint Laboratory - Complex Matrices Molecular Characterization [iC2MC], Université de Rouen Normandie [UNIROUEN], Chimie Organique et Bioorganique : Réactivité et Analyse [COBRA], Laboratoire Avancé de Spectroscopie pour les Intéractions la Réactivité et l'Environnement - UMR 8516 [LASIRE], and TOTAL Research & Technology Gonfreville [TRTG]
- Subjects
[CHIM.THEO]Chemical Sciences/Theoretical and/or physical chemistry - Abstract
International audience; Among the various alternatives to fossil energies, microalga-based fuels are promising solutions. Thanks to their ability to grow under harsh conditions and trap industrial exhaust gases, these microalgae can help reduce global warming effects. One efficient way to process this feedstock is to use hydrothermal liquefaction (HTL) which leads to an intermediate bio-crude and a residual solid. This bio-crude can be further refined to produce usable biofuel by eliminating problematic heteroatoms such as nitrogen, oxygen, and metals. The residual solid, which can represent 50 % in mass is, however not useable nowadays. To valorize this insoluble fraction, the present work is focused on its molecular characterization and, in particular, on its metal content. Metals are particularly problematic for downstream processes when they are in an organic form such as porphyrins as they destroy catalysts. Identification and speciation of these metal organic species is thus needed. However, these analyses are challenging because of the high molecular diversity of these samples. Here, complementarity between electron paramagnetic resonance spectroscopy (EPR) and FTICR-MS, which is a state-of-the-art mass spectrometer, was used for the speciation of copper elements in the residual solid. A signal characteristic of a copper surrounded by four symmetric nitrogen atoms was observed in EPR, suggesting porphyrinic structures. The dynamic range of FTICR-MS broadband analyses was not sufficient to access the isotopic fine structure of the copper porphyrins. Continuous accumulation of selected ions analyses (CASI) was thus, performed to boost the dynamic range of the mass spectrometer in a narrower mass range allowed to confirm for the first time the presence of copper porphyrins in a residual solid of bio-crude. Different families of copper porphyrins were observed, and putative structures were proposed.
- Published
- 2023