MARTINA DAMIZIA

Dottoressa di ricerca

ciclo: XXXV


supervisore: Prof. Paolo De Filippis

Titolo della tesi: Pure hydrogen production by chemical looping technology: use of iron as redox element and bioethanol as renewable reductant

The use of hydrogen as an alternative energy carrier is a promising solution to overcome the global warming issues. Hydrogen is light, storable, energy-dense, and when burned it produces no emissions of pollutants or greenhouse gases. However, since it is not naturally available, the environmental impact of hydrogen is closely linked to the type of source used for its production. The 96% of the commercial H2, mainly used in chemical and petrochemical sectors, is produced from fossil fuels, resulting globally in 900 Mt of CO2 per years. The study and optimization of alternative hydrogen production technologies based on renewable sources is therefore essential to make hydrogen a green fuel and to achieve the Zero-Net Emissions target of 2050. One of the most interesting applications of H2 as alternative and clean fuel is in the in the automotive sector, which up to now contribute for a large part to global CO2 emissions. The use of H2 in the sector of automotive is now possible thanks to the development of Fuel Cells zero-emission vehicles. Among them, Proton Exchange Membrane Fuel Cells (PEMFC) are the most promising one, able to converts the chemical energy of H2 directly into electricity already at low temperatures, with an efficiency value three times higher than internal combustion engine powered by gasoline. However, for their correct functioning, high purity hydrogen stream is required, with a strict limit on CO concentration (CO<10 ppm), a poison of the Pt-based fuel cell catalyst. Chemical looping hydrogen (CLH) technology allows the direct production of pure hydrogen in a totally green way. The process is based on the ability of iron oxides to transfer oxygen atoms between a fuel and an oxidant, maintaining constant its activity for high number of redox cycles. The process is composed by two steps: the iron oxides is first reduced to the metal form by feeding a fuel and then Fe is oxidized by steam to produce pure hydrogen and to restore the iron oxides, which participate in a subsequent redox cycle. The absence of purification units makes the CLH process suitable for the decentralized small-scale hydrogen production, solving the issues of hydrogen transportation and storage. The main purpose of this work is to demonstrate the feasibility of producing pure and green H2 by a CLH process, suitable to be directly fed to PEMFC, using bioethanol as renewable fuel. The experimental work focused on the synthesis of Fe-based materials, having high activity and high resistance to deactivation, evaluating the process efficiency in a fixed bed bench-scale plant. The influence of the operative conditions on the process efficiency was investigated, focusing the attention on the effect of different redox temperature (675°-750°C) at constant pressure (1 bar) and different flow rate of reductant fuel, with the aim of identifying the optimal conditions. The thesis is structured into 10 chapters. The first part introduces the issues related to global warming and increased energy demand, mainly based on fossil fuel. Then, chemical looping process is presented as a promising solution to overcome the criticalities of the use of H2 as fuel. The second chapter reports the recent advances in scientific literature in the field of CLH technology. Then, in Chapter 3 the experimental set-up and the synthesis methods of the iron-based oxygen carrier are described in detail; the characterization of the synthesized particles is reported in Chapter 4. In Chapter 5 the decomposition of bioethanol is studied to evaluate the feasibility of using it as renewable source of reducing agents; furthermore, tests of CLH are performed on commercial Fe2O3 powders aimed at the production of pure hydrogen by monitoring the amount of ethanol fed in reduction. Then, the influence of MnO2 addition on enhancing the iron oxides reducibility and therefore on the maximization of pure hydrogen yields is studied. In Chapter 6 the experimental results on the use of structural promoters (Al2O3, MgO and CeO2) to improve Fe oxides thermal resistance is deeply investigated focusing the attention on the influence of promoter addition on iron oxide redox activity and on the sample morphology. In Chapter 7 a dedicated study of the couple Fe/Al is performed, evaluating the influence of temperature on the process efficiency values and on Fe/Al interaction. The effect of the addition of Mn oxide to enhance the Fe oxides reduction degree and to avoid the production of hydrogen contaminated by CO, when Al2O3 is present as a structural promoter, is investigated in Chapter 8. In Chapter 9 Temperature programmed reduction (TPR) profiles of the most active samples are reported aiming to deeply study the influence of promoters in kinetics of iron oxides reduction and on the iron oxides reduction mechanism. At the end, in Chapter 10, based on the promising results obtained with OCs powders, the use of Fe-based foam, a highly porous materials suitable to be used in fixed bed reactor by keeping low pressure drop is studied with the aim of process scalability.

Produzione scientifica

11573/1724801 - 2024 - Hydrothermal Liquefaction of Organic Waste Model Compounds: The Effect of the Heating Rate on Biocrude Yield and Quality from Mixtures of Cellulose-Albumin-Sunflower Oil
Amadei, A.; Bracciale, M. P.; Damizia, M.; De Filippis, P.; De Caprariis, B.; Ferrasse, J. -H.; Scarsella, M. - 01a Articolo in rivista
rivista: ACS OMEGA (Washington, D.C. : American Chemical Society, 2016-) pp. 41194-41207 - issn: 2470-1343 - wos: WOS:001324851500001 (0) - scopus: 2-s2.0-85205924409 (0)

11573/1725264 - 2024 - Waste Reduction and Bioenergy Generation from Secondary Sludge Using Hydrothermal Liquefaction
Amadei, Alessandro; De Filippis, Paolo; Damizia, Martina; Bracciale, Maria Paola; De Caprariis, Benedetta - 01a Articolo in rivista
rivista: CHEMICAL ENGINEERING TRANSACTIONS (Milano : Sauro Pierucci Milano : AIDIC) pp. 547-552 - issn: 2283-9216 - wos: (0) - scopus: 2-s2.0-85197410166 (0)

11573/1708587 - 2024 - Chemical Recycling of Cellulose Acetate Eyewear Industry Waste by Hydrothermal Treatment
Bracciale, Maria Paola; De Caprariis, Benedetta; Musivand, Sogand; Damizia, Martina; De Filippis, Paolo - 01a Articolo in rivista
rivista: INDUSTRIAL & ENGINEERING CHEMISTRY RESEARCH (American Chemical Society:1155 Sixteenth Street Northwest:Washington, DC 20036:(800)227-5558, EMAIL: service@acs.org, INTERNET: http://www.pubs.acs.org, Fax: (614)447-3671) pp. 5078-5088 - issn: 0888-5885 - wos: WOS:001187265100001 (2) - scopus: 2-s2.0-85188135995 (2)

11573/1724765 - 2024 - Methane pyrolysis in molten media: The interplay of physical properties and catalytic activity on carbon and hydrogen production
Busillo, Emmanuel; Damizia, Martina; De Filippis, Paolo; De Caprariis, Benedetta - 01a Articolo in rivista
rivista: JOURNAL OF ANALYTICAL AND APPLIED PYROLYSIS (Elsevier BV:PO Box 211, 1000 AE Amsterdam Netherlands:011 31 20 4853757, 011 31 20 4853642, 011 31 20 4853641, EMAIL: nlinfo-f@elsevier.nl, INTERNET: http://www.elsevier.nl, Fax: 011 31 20 4853598) pp. - - issn: 0165-2370 - wos: WOS:001319711100001 (0) - scopus: 2-s2.0-85204371730 (0)

11573/1724770 - 2024 - Methane cracking in molten tin for hydrogen and carbon production—a comparison with homogeneous gas phase process
Busillo, Emmanuel; De Caprariis, Benedetta; Bracciale, Maria Paola; Cosentino, Vittoria; Damizia, Martina; Iaquaniello, Gaetano; Palo, Emma; De Filippis, Paolo - 01a Articolo in rivista
rivista: FRONTIERS OF CHEMICAL SCIENCE AND ENGINEERING (Beijing : Higher Education Press Springer) pp. - - issn: 2095-0179 - wos: WOS:001204498200001 (2) - scopus: 2-s2.0-85190417326 (2)

11573/1717438 - 2024 - Red mud as hydrogen producer in hydrothermal liquefaction of pinewood: Minimization of process wastes by recycling the water and hydrochar phases
Damizia, M.; Bracciale, M. P.; Mousavi, S.; Tai, L.; De Filippis, P.; De Caprariis, B. - 01a Articolo in rivista
rivista: RENEWABLE ENERGY (Oxford UK: Elsevier Science Limited) pp. 1-10 - issn: 0960-1481 - wos: (0) - scopus: 2-s2.0-85200841024 (2)

11573/1703497 - 2024 - Green hydrogen production using doped Fe2O3 foams
Damizia, M.; Lloreda-Jurado, P. J.; De Filippis, P.; De Caprariis, B.; Chicardi, E.; Sepulveda, R. - 01a Articolo in rivista
rivista: INTERNATIONAL JOURNAL OF HYDROGEN ENERGY (Elsevier Science Limited:Oxford Fulfillment Center, PO Box 800, Kidlington Oxford OX5 1DX United Kingdom:011 44 1865 843000, 011 44 1865 843699, EMAIL: asianfo@elsevier.com, tcb@elsevier.co.UK, INTERNET: http://www.elsevier.com, http://www.elsevier.com/locate/shpsa/, Fax: 011 44 1865 843010) pp. 834-845 - issn: 0360-3199 - wos: WOS:001139968900001 (4) - scopus: 2-s2.0-85171655809 (5)

11573/1724800 - 2024 - Techno-economic assessment of gasoline production from Fe-assisted lignocellulosic biomass hydrothermal liquefaction process with minimized waste stream
Mousavi, S.; Damizia, M.; Hamidi, R.; De Filippis, P.; De Caprariis, B. - 01a Articolo in rivista
rivista: ENERGY CONVERSION AND MANAGEMENT (Elsevier Science Limited:Oxford Fulfillment Center, PO Box 800, Kidlington Oxford OX5 1DX United Kingdom:011 44 1865 843000, 011 44 1865 843699, EMAIL: asianfo@elsevier.com, tcb@elsevier.co.UK, INTERNET: http://www.elsevier.com, http://www.elsevier.com/locate/shpsa/, Fax: 011 44 1865 843010) pp. - - issn: 0196-8904 - wos: WOS:001308998500001 (0) - scopus: 2-s2.0-85202864222 (0)

11573/1725133 - 2024 - Syngas cleaning by chemical looping conversion of tars from hazelnut shells pyrolysis/gasification
Palone, O.; Vincenti, B.; Amadei, A.; Damizia, M.; Cedola, L.; De Caprariis, B.; Borello, D. - 01a Articolo in rivista
rivista: CHEMICAL ENGINEERING TRANSACTIONS (Milano : Sauro Pierucci Milano : AIDIC) pp. 535-540 - issn: 2283-9216 - wos: (0) - scopus: 2-s2.0-85197416915 (0)

11573/1689814 - 2023 - Hydrothermal liquefaction of waste biomass model compounds. a study to unravel the complexity of Interactions in biocrude production from mixtures of cellulose-albumin-lipids
Amadei, Alessandro; De Filippis, Paolo; Damizia, Martina; Bracciale, Maria Paola; De Caprariis, Benedetta - 01a Articolo in rivista
rivista: CHEMICAL ENGINEERING TRANSACTIONS (Milano : Sauro Pierucci Milano : AIDIC) pp. - - issn: 2283-9216 - wos: (0) - scopus: 2-s2.0-85163497447 (0)

11573/1679691 - 2023 - Efficient utilization of Al2O3 as structural promoter of Fe into 2 and 3 steps chemical looping hydrogen process. Pure H2 production from ethanol
Damizia, Martina; Bracciale, Maria P.; Anania, Francesco; Tai, Lingyu; De Filippis, Paolo; De Caprariis, Benedetta - 01a Articolo in rivista
rivista: INTERNATIONAL JOURNAL OF HYDROGEN ENERGY (Elsevier Science Limited:Oxford Fulfillment Center, PO Box 800, Kidlington Oxford OX5 1DX United Kingdom:011 44 1865 843000, 011 44 1865 843699, EMAIL: asianfo@elsevier.com, tcb@elsevier.co.UK, INTERNET: http://www.elsevier.com, http://www.elsevier.com/locate/shpsa/, Fax: 011 44 1865 843010) pp. - - issn: 0360-3199 - wos: WOS:001114405800001 (5) - scopus: 2-s2.0-85153529150 (6)

11573/1682326 - 2023 - Advances in molten media technologies for methane pyrolysis
De Caprariis, Benedetta; Damizia, Martina; Busillo, Emmanuel; De Filippis, Paolo - 02a Capitolo o Articolo
libro: Turquoise Hydrogen: an effective pathway to decarbonization and value-added carbon materials - ()

11573/1667140 - 2023 - Catalytic hydrothermal liquefaction of Brachychiton populneus biomass for the production of high-value bio-crude
Eladnani, Ikram; Bracciale, Maria Paola; Damizia, Martina; Mousavi, Seyedmohammad; De Filippis, Paolo; Lakhmiri, Rajae; De Caprariis, Benedetta - 01a Articolo in rivista
rivista: PROCESSES (Basel: MDPI) pp. - - issn: 2227-9717 - wos: WOS:000941792600001 (4) - scopus: 2-s2.0-85149131337 (6)

11573/1703501 - 2023 - Recent developments and future outlooks of hydrodynamic cavitation as an intensification technology for renewable biofuels production
Hamidi, R.; Damizia, M.; De Filippis, P.; Patrizi, D.; Verdone, N.; Vilardi, G.; De Caprariis, B. - 01a Articolo in rivista
rivista: JOURNAL OF ENVIRONMENTAL CHEMICAL ENGINEERING (Amsterdam : Elsevier) pp. - - issn: 2213-3437 - wos: WOS:001080051800001 (9) - scopus: 2-s2.0-85169844293 (10)

11573/1683075 - 2023 - Simulation on hydrothermal liquefaction of pinewood to produce bio-crude in a zero-waste process scheme
Mousavi, Seyedmohammad; De Caprariis, Benedetta; Damizia, Martina; Bracciale M., Paola; De Filippis, Paolo - 01a Articolo in rivista
rivista: CHEMICAL ENGINEERING TRANSACTIONS (Milano : Sauro Pierucci Milano : AIDIC) pp. 109-114 - issn: 2283-9216 - wos: (0) - scopus: 2-s2.0-85163421176 (1)

11573/1687535 - 2023 - Viable Recycling of Polystyrene via Hydrothermal Liquefaction and Pyrolysis
Musivand, S.; Bracciale, M. P.; Damizia, M.; De Filippis, P.; De Caprariis, B. - 01a Articolo in rivista
rivista: ENERGIES (Basel : Molecular Diversity Preservation International) pp. 4917- - issn: 1996-1073 - wos: WOS:001028669500001 (2) - scopus: 2-s2.0-85164905530 (4)

11573/1660742 - 2022 - Clean syngas and hydrogen co-production by gasification and chemical looping hydrogen process using MgO-Doped Fe2O3 as redox material
Bracciale, Mp; Damizia, M; De Filippis, P; De Caprariis, B - 01a Articolo in rivista
rivista: CATALYSTS (Basel: Molecular Diversity Preservation International) pp. - - issn: 2073-4344 - wos: WOS:000872741400001 (6) - scopus: 2-s2.0-85140848586 (6)

11573/1668676 - 2022 - Utilization of al2o3 and mgo as structural promoters of fe into 2 and 3 steps chemical looping hydrogen process: pure and green h2 production
Damizia, M.; De Caprariis, B.; Bracciale, M. P.; Anania, F.; D'alvia, L.; Del Prete, Z.; De Filippis, P. - 04b Atto di convegno in volume
congresso: 23rd World Hydrogen Energy Conference: Bridging Continents by H2, WHEC 2022 (Istanbul , turkey)
libro: Proceedings of WHEC 2022 - 23rd World Hydrogen Energy Conference: Bridging Continents by H2 - (9786250008430)

11573/1682323 - 2022 - Hydrothermal Liquefaction of Biomass using Waste Material as Catalyst: Effect on the Bio-crude Yield and Quality
De Caprariis, B.; Damizia, M.; Tai, L.; De Filippis, P. - 01a Articolo in rivista
rivista: CHEMICAL ENGINEERING TRANSACTIONS (Milano : Sauro Pierucci Milano : AIDIC) pp. 607-612 - issn: 2283-9216 - wos: (0) - scopus: 2-s2.0-85133704861 (7)

11573/1620452 - 2022 - Hydrotreating of oak wood bio-crude using heterogeneous hydrogen producer over Y zeolite catalyst synthesized from rice husk
Hamidi, R.; Tai, L.; Paglia, L.; Scarsella, M.; Damizia, M.; De Filippis, P.; Musivand, S.; De Caprariis, B. - 01a Articolo in rivista
rivista: ENERGY CONVERSION AND MANAGEMENT (Elsevier Science Limited:Oxford Fulfillment Center, PO Box 800, Kidlington Oxford OX5 1DX United Kingdom:011 44 1865 843000, 011 44 1865 843699, EMAIL: asianfo@elsevier.com, tcb@elsevier.co.UK, INTERNET: http://www.elsevier.com, http://www.elsevier.com/locate/shpsa/, Fax: 011 44 1865 843010) pp. - - issn: 0196-8904 - wos: WOS:000772626800002 (10) - scopus: 2-s2.0-85124411322 (10)

11573/1658908 - 2022 - Physical-chemical characterization of different carbon-based sorbents for environmental applications
Marzeddu, Simone; Alejandra Décima, María; Camilli, Luca; Bracciale, Maria Paola; Genova, Virgilio; Paglia, Laura; Marra, Francesco; Damizia, Martina; Stoller, Marco; Chiavola, Agostina; Boni, Maria Rosaria - 01a Articolo in rivista
rivista: MATERIALS (Basel: Molecular Diversity Preservation International-MDPI) pp. - - issn: 1996-1944 - wos: WOS:000875157300001 (13) - scopus: 2-s2.0-85140842234 (17)

11573/1612893 - 2022 - Guaiacol hydrotreating with in-situ generated hydrogen over ni/modified zeolite supports
Tai, L.; Hamidi, R.; De Caprariis, B.; Damizia, M.; Paglia, L.; Scarsella, M.; Karimzadeh, R.; De Filippis, P.; Musivand, S. - 01a Articolo in rivista
rivista: RENEWABLE ENERGY (Oxford UK: Elsevier Science Limited) pp. 647-658 - issn: 0960-1481 - wos: WOS:000714438500001 (14) - scopus: 2-s2.0-85117734769 (16)

11573/1612884 - 2022 - Co-treatment of plastics with subcritical water for valuable chemical and clean solid fuel production
Tai, L.; Musivand, S.; De Caprariis, B.; Damizia, M.; Hamidi, R.; Ma, W.; De Filippis, P. - 01a Articolo in rivista
rivista: JOURNAL OF CLEANER PRODUCTION (Oxford : ELSEVIER SCI LTD Oxford : Butterworth-Heinemann, 1993-) pp. - - issn: 0959-6526 - wos: WOS:000809648000005 (14) - scopus: 2-s2.0-85123028032 (18)

11573/1571383 - 2021 - High thermal stability fe system to produce renewable pure hydrogen in steam iron process
Damizia, M.; Bracciale, M. P.; De Caprariis, B.; Genova, V.; De Filippis, P. - 01a Articolo in rivista
rivista: CHEMICAL ENGINEERING TRANSACTIONS (Milano : Sauro Pierucci Milano : AIDIC) pp. 547-552 - issn: 2283-9216 - wos: (0) - scopus: 2-s2.0-85109561998 (0)

11573/1606342 - 2021 - The role of Al2O3, MgO and CeO2 addition on steam iron process stability to produce pure and renewable hydrogen
De Caprariis, B.; Damizia, M.; De Filippis, P.; Bracciale, M. P. - 01a Articolo in rivista
rivista: INTERNATIONAL JOURNAL OF HYDROGEN ENERGY (Elsevier Science Limited:Oxford Fulfillment Center, PO Box 800, Kidlington Oxford OX5 1DX United Kingdom:011 44 1865 843000, 011 44 1865 843699, EMAIL: asianfo@elsevier.com, tcb@elsevier.co.UK, INTERNET: http://www.elsevier.com, http://www.elsevier.com/locate/shpsa/, Fax: 011 44 1865 843010) pp. 39067-39078 - issn: 0360-3199 - wos: WOS:000717444600010 (11) - scopus: 2-s2.0-85117246191 (12)

11573/1449669 - 2021 - Pure hydrogen production by steam-iron process. The synergic effect of MnO2 and Fe2O3
De Filippis, P.; D'alvia, L.; Damizia, M.; De Caprariis, B.; Del Prete, Z. - 01a Articolo in rivista
rivista: INTERNATIONAL JOURNAL OF ENERGY RESEARCH (John Wiley & Sons Limited:1 Oldlands Way, Bognor Regis, P022 9SA United Kingdom:011 44 1243 779777, EMAIL: cs-journals@wiley.co.uk, INTERNET: http://www.wiley.co.uk, Fax: 011 44 1243 843232) pp. 4479-4494 - issn: 0363-907X - wos: WOS:000581890600001 (12) - scopus: 2-s2.0-85093497538 (16)

11573/1657147 - 2020 - PRELIMINARY EFFICIENCY MEASUREMENTS OF A PURE HYDROGEN PRODUCTION PROCESS
D'alvia, Livio; Damizia, M.; De Caprariis, B.; Rizzuto, E.; De Filippis, P.; Del Prete, Z. - 04d Abstract in atti di convegno
congresso: IV Forum Nazionale delle Misure, (ONLINE)
libro: Atti del IV Forum Nazionale delle Misure, - ()

11573/1342988 - 2020 - Unsupported Ni metal catalyst in hydrothermal liquefaction of oak wood. Effect of catalyst surface modification
De Caprariis, B.; Bracciale, M. P.; Bavasso, I.; Chen, G.; Damizia, Martina; Genova, V.; Marra, F.; Paglia, L.; Pulci, G.; Scarsella, M.; Tai, L.; De Filippis, P. - 01a Articolo in rivista
rivista: SCIENCE OF THE TOTAL ENVIRONMENT (Elsevier BV:PO Box 211, 1000 AE Amsterdam Netherlands:011 31 20 4853757, 011 31 20 4853642, 011 31 20 4853641, EMAIL: nlinfo-f@elsevier.nl, INTERNET: http://www.elsevier.nl, Fax: 011 31 20 4853598 Tokyo ; Oxford ; Lausanne ; New York ; Shannon ; Amsterdam : Elsevier) pp. - - issn: 0048-9697 - wos: WOS:000512281700129 (34) - scopus: 2-s2.0-85078737081 (42)

11573/1438467 - 2020 - Heterogeneous catalysts for hydrothermal liquefaction of lignocellulosic biomass. A review
Scarsella, M.; De Caprariis, B.; Damizia, M.; De Filippis, P. - 01a Articolo in rivista
rivista: BIOMASS & BIOENERGY (Oxford; New York: Pergamon, Amsterdam: Elsevier) pp. - - issn: 0961-9534 - wos: WOS:000560059700007 (69) - scopus: 2-s2.0-85088631615 (94)

11573/1255747 - 2019 - Enhanced bio-crude yield and quality by reductive hydrothermal liquefaction of oak wood biomass. Effect of iron addition
De Caprariis, Benedetta; Bavasso, Irene; Bracciale, Maria Paola; Damizia, Martina; De Filippis, Paolo; Scarsella, Marco - 01a Articolo in rivista
rivista: JOURNAL OF ANALYTICAL AND APPLIED PYROLYSIS (Elsevier BV:PO Box 211, 1000 AE Amsterdam Netherlands:011 31 20 4853757, 011 31 20 4853642, 011 31 20 4853641, EMAIL: nlinfo-f@elsevier.nl, INTERNET: http://www.elsevier.nl, Fax: 011 31 20 4853598) pp. 123-130 - issn: 0165-2370 - wos: WOS:000462761400013 (48) - scopus: 2-s2.0-85060097776 (60)

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