TY - GEN A1 - González-Arias, Judith A1 - González-Castaño, Miriam A1 - Sánchez, Marta Elena A1 - Cara-Jiménez, Jorge A1 - Arellano-García, Harvey T1 - Valorization of biomass-derived CO2 residues with Cu-MnOx catalysts for RWGS reaction T2 - Renewable Energy N2 - This study delivers useful understanding towards the design of effective catalytic systems for upgrading real CO2erich residual streams derived from biomass valorization. Within this perspective, a catalysts' series based on (5 wt%) Cu - (X wt%) Mn/Al2O3with X¼0, 3, 8, and 10 is employed. The improved catalyst performance achieved through Mn incorporation is ascribed to enhanced Cu dispersions and promoted surface basic concentrations. Under standard RWGS conditions, the highest reaction rates achieved by(5 wt%) Cu - (8 wt%) Mn/Al2O3catalyst were associated to improved Cu dispersions along with the constitution of highly active Cu-MnOxdomains. Remarkably, variations on the optimal Cu to Mn ratios were detected as a function of the RWGS reaction conditions. Thus, under simulated CO2-rich residual feedstock's, i.e., in presence of CO and CH4, the further promotion on the Cu dispersion attained by the larger amounts of MnOxrendered the (5 wt%) Cu - (10 wt%) Mn/Al2O3catalyst as the best performing sample. Overall, the presented outcomes underline operative strategies for developing catalytic systems with advanced implementation potentialities. KW - CO2 waste valorization KW - CO2-Rich residues KW - Reverse water gas shift KW - CO2 reduction KW - Cu-catalysts KW - Manganese oxide Y1 - 2022 U6 - https://doi.org/10.1016/j.renene.2021.10.029 SN - 1879-0682 IS - 182 SP - 443 EP - 451 ER - TY - GEN A1 - González-Arias, Judith A1 - Baena-Moreno, Francisco Manuel A1 - González-Castaño, Miriam A1 - Arellano-García, Harvey T1 - Economic approach for CO2 valorization from hydrothermal carbonization gaseous streams via reverse water-gas shift reaction T2 - Fuel N2 - In this work the economic performance of valorizing the gaseous stream coming from hydrothermal carbonization (HTC) of olive tree pruning is presented as a novel strategy to improve the competitiveness of HTC. The valorization of the commonly disregarded gaseous stream produced in this thermochemical treatment was proposed via the Reverse Water–Gas Shift reaction. This allows to obtain syngas for selling and therefore improving the overall economic performance of the process. To this end, three plant sizes were selected (312.5, 625 and 1250 kg/h of biomass processing). The parameters with a higher share in the total cost distribution along with the revenues from the hydrochar and the syngas selling were further evaluated. The results evidenced that with the assumptions taken, the overall process is still not profitable. To reach profitability, syngas selling prices between 2.2 and 3.4 €/m3 are needed, revealing that this proposal is not economically attractive. Alternatively, a lack of competitiveness in the current market is revealed with hydrochar selling prices between 0.41 and 0.64 €/kg to make the project profitable. The catalyst cost, sharing approximately 20% of the total cost, is the parameter with the highest impact in the total economics of the process. The second one is the hydrogen price production, representing almost 16% of the total. Investment subsidies are also examined as a potential tool to cover part of the initial investment. These results evidenced that further efforts and measures are needed to push forward in the path towards circular economy societies. KW - Hydrothermal carbonization KW - CO2 waste valorization KW - Reverse water gas shift KW - Profitability analysis Y1 - 2022 U6 - https://doi.org/10.1016/j.fuel.2021.123055 SN - 0016-2361 VL - 313 SP - 1 EP - 7 ER - TY - GEN A1 - Tarifa, Pilar A1 - González-Castaño, Miriam A1 - Cazaña, F. A1 - Monzón, Antonio A1 - Arellano-García, Harvey T1 - Development of one-pot Cu/cellulose derived carbon catalysts for RWGS reaction T2 - Fuel N2 - A series of Cu-based catalysts promoted with Fe, Ce and Al supported on cellulose derived carbon (CDC) was prepared by biomorphic mineralization technique for the RWGS reaction. The excellent Cu dispersions (7 nm at ca. 30 wt% Cu) along with the resilience toward metal sintering attained in the entire catalysts series highlight one-pot decomposition of cellulose under reducing atmosphere as an excellent synthesis method which enable obtaining well-dispersed Cu nanoparticles. The influence of incorporating a second metal oxide over biomorphic mineralized Cu systems was also investigated. With the Cu-Ce system exhibiting the best catalyst performance of the catalysts’ series, the enhanced catalyst performances were majorly ascribed to the catalysts redox properties. The lineal relationships stablished between oxygen exchange capacity and CO2 conversion rates remarks the employed sequential H2/CO2 cycles as an effective methodology for screening the catalytic performance of Cu catalysts for RWGS reaction. KW - RWGS KW - Cu catalysts KW - Oxygen exchange capacity KW - Cellulose derived carbon Y1 - 2022 U6 - https://doi.org/10.1016/j.fuel.2022.123707 SN - 0016-2361 VL - Vol. 319 ER - TY - GEN A1 - Mahmood, Safdar A1 - González-Castaño, Miriam A1 - Penkova, Anna A1 - Centeno, Miguel Angel A1 - Odriozola, José Antonio A1 - Arellano-García, Harvey T1 - CO2 methanation on Ni/YMn1-xAlxO3 perovskite catalysts T2 - Applied Materials Today N2 - Seeking for advanced catalytic systems for the CO2 methanation reaction, the use of Ni supported catalysts over redox materials is often proposed. Profiting the superior redox properties described for layered perovskite systems, this work has investigated a series Ni supported YMn1-xAlxO3 (x = 0, 0.2, 0.5, 0.8, 1) perovskite catalysts. The obtained results evidenced the impact of the support nature on the systems redox properties and Ni-support interactions. Within the catalysts series, the greater methanation rates displayed by Ni/YMn0.5Al0.5O3 catalyst (0.748 mmolCO2,conv.s–1 gNi –1 at 400 ◦C and 60 L/gh) were associated to the interplay between the support redox properties and superior Ni dispersion. The improved redox behavior attained through the Al-incorporation (up to x = 0.5) was associated to the layered perovskite structures which, being distorted and constituted by smaller crystal sizes, facilitated the behavior of Mn redox couples as surface species readily interconverted. Exhibiting catalytic performances comparable to precious metals based catalysts, this work proposes the Ni/YMn0.5Al0.5O3 catalyst as an effective system for the CO2 methanation reaction. KW - CO2 methanation KW - Perovskites KW - Ni catalyst KW - Manganese KW - Aluminium Y1 - 2022 U6 - https://doi.org/10.1016/j.apmt.2022.101577 SN - 2352-9407 VL - 29 SP - 1 EP - 11 ER - TY - GEN A1 - González-Castaño, Miriam A1 - Baena-Moreno, Francisco Manuel A1 - Navarro de Miguel, Juan Carlos A1 - Miah, Kamal Uddin Mohammad A1 - Arroyo-Torralvo, Fátima A1 - Ossenbrink, Ralf A1 - Odriozola, José Antonio A1 - Benzinger, Walther A1 - Hensel, Andreas A1 - Wenka, Achim A1 - Arellano-García, Harvey T1 - 3D-printed structured catalysts for CO2 methanation reaction: Advancing of gyroid-based geometries T2 - Energy Conversion and Management N2 - This work investigates the CO2 methanation rate of structured catalysts by tuning the geometry of 3D-printed metal Fluid Guiding Elements (FGEs) structures based on periodically variable pseudo-gyroid geometries. The enhanced performance showed by the structured catalytic systems is mostly associated with the capability of the FGEs substrate geometries for efficient heat usages. Thus, variations on the channels diameter resulted in ca. 25% greater CO2 conversions values at intermediate temperature ranges. The highest void fraction evidenced in the best performing catalyst (3D-1) favored the radial heat transfer and resulted in significantly enhanced catalytic activity, achieving close to equilibrium (75%) conversions at 400 ◦C and 120 mL/min. For the 3D-1 catalyst, a mathematical model based on an experimental design was developed thus enabling the estimation of its behavior as a function of temperature, spatial velocity, hydrogen to carbon dioxide (H2/CO2) ratio, and inlet CO2 concentration. Its optimal operating conditions were established under 3 different scenarios: 1) no restrictions, 2) minimum H2:CO2 ratios, and 3) minimum temperatures and H2/CO2 ratio. For instance, for the lattest scenario, the best CO2 methanation conditions require operating at 431 ◦C, 200 mL/min, H2/CO2 = 3 M ratio, and inlet CO2 concentration = 10 %. KW - 3D-printing KW - Triply periodic minimal surfaces KW - Fluid guiding elements KW - CO2 methanation KW - Structured catalysts KW - Experiment design Y1 - 2022 U6 - https://doi.org/10.1016/j.enconman.2022.115464 SN - 2590-1745 VL - 258 ER - TY - GEN A1 - Medina Méndez, Juan Ali A1 - González-Castaño, Miriam A1 - Baena-Moreno, Francisco Manuel A1 - Arellano-García, Harvey ED - Kmiotek, M. ED - Kordos, A. T1 - CO2 methanation: on the modeling of reacting laminar flows in structured Ni/MgAl2O4 catalysts T2 - XXV Fluid Mechanics Conference, Rzeszów, Poland, 7-9 September 2022, Book of Abstracts Y1 - 2022 SN - 978-83-7934-590-8 SP - 98 EP - 100 PB - Publishing House of Rzeszów University of Technology CY - Rzeszów, Poland ER - TY - GEN A1 - Medina Méndez, Juan Ali A1 - González-Castaño, Miriam A1 - Baena-Moreno, Francisco Manuel A1 - Arellano-García, Harvey T1 - CO2 methanation: on the modeling of reacting laminar flows in structured Ni/MgAl2O4 catalysts T2 - Journal of Physics: Conference Series Y1 - 2022 UR - https://iopscience.iop.org/article/10.1088/1742-6596/2367/1/012015 U6 - https://doi.org/10.1088/1742-6596/2367/1/012015 IS - 2367 PB - IOP Publishing ER - TY - GEN A1 - Miah, Kamal Uddin Mohammad A1 - Kloshek, Alexander A1 - González-Castaño, Miriam A1 - Kehm, Christian A1 - Ossenbrink, Ralf A1 - Michailov, Vesselin T1 - Herstellen hocheffektiver Mikroreaktoren durch selektives Laserstrahlschmelzen T2 - DVS Congress 2022, Große Schweißtechnische Tagung, DVS Campus ; Kurzfassungen der Vorträge der Veranstaltung in Koblenz vom 19. bis 21. September 2022 ; (Langfassungen der Beiträge auf USB-Karte) N2 - Das pulverbasierte 3D-Metalldrucken ermöglicht die Fertigung von hochkomplexen Integralbauteilen, die als Trägerstruktur für Mikroreaktoren benutzt werden. Nach einer Beschichtung der Struktur mit einem Katalysatormaterial, können diese Mikroreaktoren höchst effizient für die CO2-Methanisierung eingesetzt werden. Durch die additive Fertigung mit dem selektiven Laserstrahlschmelzen (SLM) wurden adaptierte dreidimensionale periodische Gitterstrukturen mit sehr geringen Wandstärken hergestellt. Diese weisen ein sehr günstiges Verhältnis von Oberfläche zu Volumen (TPMS - Triply periodic minimal surface) auf. Des Weiteren zeigen die TPMS-Strukturen vorteilhafte Strömungseigenschaften, die sowohl für die Beschichtung mit dem Katalysator-Material als auch die Durchströmung mit den Reaktionsmedien im Betrieb essentiell sind. So ist es beispielsweise möglich, durch die Variation der Dimension einer TPMS-Struktur die Oberfläche pro Volumeneinheit, den hydraulischen Durchmesser des Reaktors und somit auch den Transportprozess des Fluids deutlich zu verbessern. Diese Faktoren ermöglichen eine effektivere Gas-Katalysator-Reaktion. Im Vergleich zu Mikroreaktorstrukturen aus den traditionellen Herstellungsverfahren liefern die additiv gefertigten Strukturen sowohl eine höhere CO2-Umwandlungsrate als auch eine CH4-Selektivität innerhalb des diffusionskontrollierten Bereichs. Y1 - 2022 SN - 978-3-96144-189-1 SP - 708 EP - 713 PB - DVS Media GmbH CY - Düsseldorf ER - TY - GEN A1 - Tarifa, Pilar A1 - Ramirez Reina, Tomas A1 - González-Castaño, Miriam A1 - Arellano-García, Harvey T1 - Catalytic Upgrading of Biomass-Gasification Mixtures Using Ni-Fe/MgAl₂O₄ as a Bifunctional Catalyst T2 - Energy and Fuels N2 - Biomass gasification streams typically contain a mixture of CO, H2, CH4, and CO2 as the majority components and frequently require conditioning for downstream processes. Herein, we investigate the catalytic upgrading of surrogate biomass gasifiers through the generation of syngas. Seeking a bifunctional system capable of converting CO2 and CH4 to CO, a reverse water gas shift (RWGS) catalyst based on Fe/MgAl2O4 was decorated with an increasing content of Ni metal and evaluated for producing syngas using different feedstock compositions. This approach proved efficient for gas upgrading, and the incorporation of adequate Ni content increased the CO content by promoting the RWGS and dry reforming of methane (DRM) reactions. The larger CO productivity attained at high temperatures was intimately associated with the generation of FeNi3 alloys. Among the catalysts' series, Ni-rich catalysts favored the CO productivity in the presence of CH4, but important carbon deposition processes were noticed. On the contrary, 2Ni-Fe/MgAl2O4 resulted in a competitive and cost-effective system delivering large amounts of CO with almost no coke deposits. Overall, the incorporation of a suitable realistic application for valorization of variable composition of biomass-gasification derived mixtures obtaining a syngas-rich stream thus opens new routes for biosyngas production and upgrading. Y1 - 2022 UR - https://pubs.acs.org/doi/10.1021/acs.energyfuels.2c01452 U6 - https://doi.org/10.1021/acs.energyfuels.2c01452 SN - 1520-5029 SN - 0887-0624 VL - 36 IS - 15 SP - 8267 EP - 8273 ER - TY - GEN A1 - Bobadilla, Luis F. A1 - Azancot, Lola A1 - Luque-Alvarez, Ligia A. A1 - Torres-Sempere, Guillermo A1 - Gonzalez-Castano, Miriam A1 - Pastor-Perez, Laura A1 - Yu, Jie A1 - Ramirez Reina, Tomas A1 - Ivanova, Svetlana A1 - Centeno, Miguel Angel A1 - Odriozola, José Antonio T1 - Development of Power-to-X Catalytic Processes for CO2 Valorisation: From the Molecular Level to the Reactor Architecture T2 - Chemistry N2 - Nowadays, global climate change is likely the most compelling problem mankind is facing. In this scenario, decarbonisation of the chemical industry is one of the global challenges that the scientific community needs to address in the immediate future. Catalysis and catalytic processes are called to play a decisive role in the transition to a more sustainable and low-carbon future. This critical review analyses the unique advantages of structured reactors (isothermicity, a wide range of residence times availability, complex geometries) with the multifunctional design of efficient catalysts to synthesise chemicals using CO2 and renewable H2 in a Power-to-X (PTX) strategy. Fine-chemistry synthetic methods and advanced in situ/operando techniques are essential to elucidate the changes of the catalysts during the studied reaction, thus gathering fundamental information about the active species and reaction mechanisms. Such information becomes crucial to refine the catalyst’s formulation and boost the reaction’s performance. On the other hand, reactors architecture allows flow pattern and temperature control, the management of strong thermal effects and the incorporation of specifically designed materials as catalytically active phases are expected to significantly contribute to the advance in the valorisation of CO2 in the form of high added-value products. From a general perspective, this paper aims to update the state of the art in Carbon Capture and Utilisation (CCU) and PTX concepts with emphasis on processes involving the transformation of CO2 into targeted fuels and platform chemicals, combining innovation from the point of view of both structured reactor design and multifunctional catalysts development. Y1 - 2022 UR - https://www.mdpi.com/2624-8549/4/4/83 U6 - https://doi.org/10.3390/chemistry4040083 SN - 2624-8549 VL - 4 IS - 4 SP - 1250 EP - 1280 ER -