Doctoral School in Chemistry and Materials Science
XXXI Cycle (2015-2018)
REPORT OF THE ACTIVITIES UNDERTAKEN
Candidate: Sara Fulignati Date of Birth: 01/08/1990 Place of Birth: Pisa
Supervisors: Prof. Anna Maria Raspolli Galletti and Prof. Claudia Antonetti
Title of PhD Thesis: Platform-chemicals synthesis through selective hydrogenation of chemical intermediates from renewable resources.
Research project: The necessity of replacing fossil resources with renewable ones makes the catalytic conversion of these last a real challenge for the industrial chemistry. In this perspective, 5-hydroxymethylfurfural (HMF) is a key molecule because it could be obtained from renewable resources, such as the lignocellulosic biomass, and, due to its functionality, it could be a precursor of important monomers, biofuels and chemicals. Under this perspective, the present project has two main goals: i) the optimization of HMF synthesis from monosaccharides, polysaccharides and raw biomasses, and ii) the optimization of HMF conversion to valuable products under the most sustainable reaction conditions. Regarding the synthesis of HMF, it was carried out starting from fructose, inulin and Jerusalem artichoke adopting water as reaction medium under microwave irradiation. The reaction was performed in the presence of both heterogeneous catalysts (niobium and zirconium phosphates and acid resin Amberlyst-70) and a wide range of homogeneous catalysts, such as metal salts. The influence of the reaction parameters was investigated and in the presence of the most promising catalytic systems the reaction conditions had been optimized through a statistical modelling of Response Surface Methodology. At the end of the HMF synthesis, a solid by-product, called humins, was recovered and it was characterized through analytical techniques (Py/GC-MS and EGA-MS) in order to investigate its chemical composition. Once optimized the synthesis of HMF, its conversion to valuable products involved the hydrogenation reaction to two important monomers, such as 2,5-bis(hydroxymethyl)furan (BHMF) and
2,5-bis(hydroxymethyl)tetrahydrofuran (BHMTHF). Also in this case the reaction was carried out in respect of Green Chemistry principles, working with heterogeneous catalysts and water as solvent. Their synthesis was optimized in batch reactor starting from both pure HMF and crude hydrolyzate obtained from fructose through a cascade process, which makes the reaction cheaper and more sustainable. The hydrogenation of HMF to BHMF and BHMTHF was also optimized in a flow reactor, being more interesting under an industrial point of view. In addition, the flow setup allows the study of important physical phenomena, such as the mass transfer intraparticle limitation of the reactants. At the end, in all the investigated reactions the recyclability of catalysts and their reactivation were investigated.
FORMATIVE ACTIVITIES: 1st year (academic year 2015-2016) Attended courses:
• E4AC-English for Academics; Adrian Wallwork (20 h); • Chemiometria; Francesca Modugno (24 h);
• PhD+ UNIPI; Several Professors (18 h) Attended seminars:
• “Selective strong bond cleavage catalysed by transition metal complex”; Hiroshi Nakazawa (2 h);
• “Impatto delle tecniche microfluidiche in (radio)chimica”; Giancarlo Pascali (2 h);
• “Tecnica Raman e potenzialità dello strumento XploRA™PLUS”; Horiba Scientific (2 h).
2nd year (academic year 2016-2017) Attended courses:
• Chemometrics; Marco Calderisi (8 h) Attended seminars:
• “REALCAT: discover today the catalysts of tomorrow”; Egon Heuson (2 h)
• “Workshop on waste valorization as raw material in packaging and agricultural material preparation”; IPCF-CNR (8 h)
• Metal catalyzed cross coupling reactions and role of ligands; Debabrata Maiti (2 h) Attended seminars:
• “L’uso dei fitofarmaci nell’ortoflorovivaismo dal punto di vista dell’agronomo”; Luca Incrocci (2 h)
RESEARCH EXPERIENCE IN OTHER INSTITUTIONS
From 12/06/2017 to 13/10/2017 the candidate stayed at University of Groningen (Groningen, Netherlands) under the supervision of Prof. H.J. Heeres where she performed the hydrogenation of 5-hydroxymethylfurfural to two important monomers, such as 2,5-bis(hydroxymethyl)furan and 2,5-bis(hydroxymethyl)tetrahydrofuran, in a flow reactor. High yields of each product were obtained under the same reaction conditions tuning the reactor space time. Moreover, the influence of the mass transfer limitation of the reactants and the stability of the catalyst were investigated.
CONFERENCES, WORKSHOPS, SEMINARS ATTENDED IN ITALY AND ABROAD • Attended the Conference XIII PhD-Chem Day (Bologna), 10-11 March 2016, with the
contribution “Catalytic valorisation of renewable resource” S. Fulignati, C. Antonetti, A. M. Raspolli Galletti, E. Ribechini.
• Attended with fellowship to the Conference XIX Congresso Nazionale di Catalisi-GIC 2016 (Bressanone), 11-14 September 2016 with the contribution “Sustainable synthesis of 5-hydroxymethyl-2-furaldehyde and analytical study of the solid by-products” S. Fulignati, C. Antonetti, D. Licursi, M. Martinelli, A. M. Raspolli Galletti, E. Ribechini, A. Massaro (awarded as the best communication of the conference).
• Attended the Conference XIV PhD-Chem Day (Bari), 30-31 March 2017 with the contribution “Catalytic conversion of biomass to platform-chemicals and exploitation of the solid residue as CO2-trapper” S. Fulignati, D. Licursi, C. Antonetti, S. Vitolo, M. Puccini, A. M. Raspolli
Galletti.
• Attended with fellowship the Conference Europacat 2017 (Firenze), 27-31 August 2017 with the contribution “Biorefinery of the hazelnut shells (Tonda Gentile Romana). Acid-catalysed hydrothermal treatment for the production of levulinic acid and hydrochar” S. Fulignati, D. Licursi, C. Antonetti, E. Ribechini, S. Vitolo, M. Puccini, A.M. Raspolli Galletti.
• Attended the Conference XV PhD-Chem Day (Trieste), 5-6 April 2018 with the contribution “Different catalytic approaches for an integrated valorization of renewable resources” S. Fulignati, C. Antonetti, D. Licursi, E. Ribechini, A. M. Raspolli Galletti,
• Attended the Conference Chemistry for the Future 2018 (Pisa), 4-6 July 2018 with the contribution “Platform-chemicals synthesis through selective hydrogenation of chemical intermediates from renewables” S. Fulignati, C. Antonetti, D. Licursi, H.J. Heeres, A.M. Raspolli Galletti.
• Attended with fellowship the Conference XX Congresso Nazionale di Catalisi- GIC 2018 (Milano), 2-5 September 2018 with the contribution “Hydrogenation of 5-hydroxymethylfurfural to diols: comparison of batch and flow reactors” S. Fulignati, C. Antonetti, D. Licursi, M. Pieraccioni, H.J. Heeres, A.M. Raspolli Galletti.
PUBLICATIONS (ARTICLES)
• C. Antonetti, D. Licursi, S. Fulignati, G. Valentini, A.M. Raspolli Galletti, “New frontiers in the catalytic synthesis of levulinic acid: from sugars to raw and waste biomass as starting feedstock”, Catalysts 2016, 6, 196-224.
• C. Antonetti, M. Melloni, D. Licursi, S. Fulignati, E. Ribechini, S. Rivas, J.C. Parajó, F. Cavani, A.M. Raspolli Galletti, “Microwave-assisted dehydration of fructose and inulin to HMF catalysed by niobium and zirconium phosphate catalysts”, Appl. Catal. B: Env. 2017, 206, 364-377.
• C. Antonetti, A.M. Raspolli Galletti, S. Fulignati, D. Licursi, “Amberlyst A-70: a surprisingly active catalyst for the MW-assisted dehydration of fructose and inulin to HMF in water”, Catal.
Commun. 2017, 97, 146-150.
• D. Licursi, C. Antonetti, S. Fulignati, S. Vitolo, M. Puccini, E. Ribechini, L. Bernazzani, A.M. Raspolli Galletti, “In-depth characterization of valuable char obtained from hydrothermal conversion of hazelnut shells to levulinic acid”, Biores. Technol. 2017, 244, 880-888.
• D. Licursi, C. Antonetti, S. Fulignati, A. Corsini, N. Boschi, A.M. Raspolli Galletti, “Smart valorization of waste biomass: exhausted lemon peels, coffee silverskins and paper wastes for the production of levulinic acid”, Chem. Eng. Trans. 2018, 65, 637-642.
• D. Licursi, C. Antonetti, S. Fulignati, M. Giannoni, A.M. Raspolli Galletti, “Cascade strategy for the tunable catalytic valorization of levulinic acid and γ-valerolactone to
2-• L. Biancalana, S. Fulignati, C. Antonetti, S. Zacchini, G. Provinciali, G. Pampaloni, A.M. Raspolli Galletti, F. Marchetti, “Ruthenium p-cymene complexes with α-diimine ligands as catalytic precursors for the transfer hydrogenation of ethyl levulinate to γ-valerolactone” New J.
Chem. 2018, 42, 17574-17586.
• C. Antonetti, D. Licursi, S. Fulignati, A.M. Raspolli Galletti, “Biofuels from waste biomass: a cascade strategy for the sustainable production of 2-methyl-tetrahydrofuran and 2-butanol”
DGMK Tagungsbericht (accepted).
• E. Balestri, V. Menicagli; V. Ligorini; S. Fulignati; A.M. Raspolli Galletti; C. Lardicci, “Phytotoxicity assessment of plastic bag leachates using the seed germination test of Lepidium sativum: conventional versus biodegradable and compostable bags”, Ecol. Indic. (accepted). • C. Antonetti, S. Fulignati, D. Licursi, A.M. Raspolli Galletti, “Turning point towards the
sustainable production of HMF in water: metal salts for its synthesis from fructose and inulin”,
ACS Sust. Chem. Eng. (accepted).
• S. Fulignati, C. Antonetti, D. Licursi, M. Pieraccioni, E. Wilbers, H.J. Heeres, A.M. Raspolli Galletti, “Tunable hydrogenation of pure and crude HMF to diols using heterogeneous catalysts”, Appl. Catal. A: Gen. (submitted).
PUBLICATIONS (PROCEEDINGS)
• XX Congresso Nazionale di Catalisi-GIC, 2-5 September 2018 (Milano) S. Fulignati, C. Antonetti, D. Licursi, M. Pieraccioni, H.J. Heeres, A.M Raspolli Galletti “Hydrogenation of 5-hydroxymethylfurfural to diols: comparison of batch and flow reactors”
• Chemistry for the Future, 4-6 July 2018 (Pisa) S. Fulignati, C. Antonetti, D. Licursi, H.J. Heeres, A.M Raspolli Galletti “Platform-chemicals synthesis through selective hydrogenation of chemical intermediates from renewables”
• XVI Convegno-Scuola Chimica dei Carboidrati, 17-20 June 2018 (Siena) N. Di Fidio, S. Fulignati, C. Antonetti, A.M Raspolli Galletti “Production of second generation of sugars from giant reed and cardoon as potential feedstock for the bioconversion into microbial lipids”
• Contributo al XV PhD-Chem Day, 5-6 April 2018 (Trieste) S. Fulignati, C. Antonetti, D. Licursi, E. Ribechini, A.M. Raspolli Galletti “Different catalytic approach for an integrated valorization of renewable resources”
• XXVI Congresso Nazionale della Società Chimica Italiana, 10-14 September 2017 (Paestum) D. Licursi, C. Antonetti, S. Fulignati, A. Corsini, A.M. Raspolli Galletti “The hydrothermal conversion of cellulose-rich wastes deriving from the papermaking process to levulinic acid as smart opportunity
for their re-use and valorization”
• Europacat 2017, 27-31 August 2017 (Firenze) C. Antonetti, S. Fulignati, D. Licursi, M. Pieraccioni, A.M. Raspolli Galletti “Sustainable catalytic valorization of fructose-derived HMF to 2,5-bis(hydroxymethyl)furan and 2,5-bis(hydroxymethyl)tetrahydrofuran”
• Europacat 2017, 27-31 August 2017 (Firenze) S. Fulignati, D. Licursi, C. Antonetti, E. Ribechini, S. Vitolo, M. Puccini, A.M. Raspolli Galletti “Biorefinery of the hazelnuth shells (Tonda Gentile Romana). Acid-catalysed hydrothermal treatment for the production of levulinic acid and hydrochar” • Chemistry for the Future, 5-7 July 2017 (Pisa) C. Antonetti, D. Licursi, S. Fulignati, S. Rivas, J.C.
Parajó, A.M. Raspolli Galletti “Sustainable expoitation of renewable sesources”
• XIV PhD-Chem Day del CIRCC-Consorzio Interuniversitario Reattività Chimica e Catalisi, 29-31 March 2017 (Bari) S. Fulignati, D. Licursi, C. Antonetti, S. Vitolo, M. Puccini, A.M. Raspolli Galletti “Catalytic conversion of biomass to platform-chemicals and exploitation of the solid residue as CO2
-trapper”
• 4° Workshop Nazionale GRUPPO INTERDIVISIONALE GREEN CHEMISTRY – CHIMICA SOSTENIBILE, 10 June 2016 (Firenze) C. Antonetti, S. Fulignati, D. Licursi, M. Martinelli, S. Rapiti, A.M. Raspolli Galletti “Della biomassa lignocellulosica non si butta via niente: esempi di valorizzazione integrale di biomasse diverse”
• XIII PhD-Chem Day del CIRCC-Consorzio Interuniversitario Reattività Chimica e Catalisi, 10-11 March 2016 (Bologna) S. Fulignati, C. Antonetti, A.M. Raspolli Galletti, E. Ribechini “Catalytic valorisation of renewable resources”
• XIX Congresso Nazionale della Divisione di Chimica Industriale della Società Chimica Italiana – Materiali e Prodotti per il futuro dell’Industria Chimica, 14-16 September 2015 (Salerno) C. Antonetti, D. Licursi, E. Bertolucci, S. Fulignati, M. Martinelli, A.M. Raspolli Galletti “Heterogeneous catalysis for the production of 5-hydroxymethyl-2-furfural and of 2,5-bis(hydroxymethyl)furan from fructose and inulin”
• 3° Workshop Nazionale GRUPPO INTERDIVISIONALE GREEN CHEMISTRY – CHIMICA SOSTENIBILE, 12 June 2015 (Napoli) C. Antonetti, D. Licursi, A.M. Raspolli Galletti, E. Ribechini, • XIX Congresso del Gruppo Interdivisionale di Catalisi della Società Chimica Italiana, 11-14 September 2016 (Bressanone) S. Fulignati, C. Antonetti, D. Licursi, M. Martinelli, A. M. Raspolli Galletti, E. Ribechini, A. Massaro “Sustainable synthesis of 5-hydroxymethyl-2-furaldehyde and analytical study of the solid by-products”
TUTORING AND SUPPLEMENTARY TEACHING ACTIVITIES Teaching seminar
“5-idrossimetil-2-furaldeide (HMF): interesse e sintesi” Tutoring for the laboratory of
“Principi di chimica industriale e laboratorio” (20 h) academic year 2016/2017 Tutoring for the laboratory of
“Principi di chimica industriale e laboratorio” (20 h) academic year 2017/2018
OTHER ACTIVITIES
• Member of the research project PRIN-2015 “Heterogeneous Robust Catalysts to Upgrade Low value biomass Streams (HERCULES)” coordinate by Prof. Angelo Vaccari (University of Bologna) in the Research Unit of Prof.ssa Anna Maria Raspolli Galletti (University of Pisa);
• Member of the research project PRA-2017 “Distretti urbani a zero impatto energetico ed ambientale” coordinate by Prof. Marco Raugi (University of Pisa);
• Reviewer for the journals Chemical Engineering Transaction; Biomass Conversion and
Biorefinery.
Sara Fulignati
