2026
Journal Articles
Mercader, V. D.; Sanz-Monreal, P.; Durán, P.; Aragüés-Aldea, P.; Francés, E.; Herguido, J.; Peña, J. A.
Intensifying synthetic natural gas production by functionalization of a NiFe/γ-Al2O3 catalyst with alkaline and alkaline-earth materials Journal Article
En: Fuel, vol. 406, pp. 136698, 2026, ISSN: 0016-2361.
@article{MERCADER2026136698,
title = {Intensifying synthetic natural gas production by functionalization of a NiFe/γ-Al2O3 catalyst with alkaline and alkaline-earth materials},
author = {V. D. Mercader and P. Sanz-Monreal and P. Durán and P. Aragüés-Aldea and E. Francés and J. Herguido and J. A. Peña},
url = {https://www.sciencedirect.com/science/article/pii/S0016236125024238},
doi = {https://doi.org/10.1016/j.fuel.2025.136698},
issn = {0016-2361},
year = {2026},
date = {2026-01-01},
journal = {Fuel},
volume = {406},
pages = {136698},
abstract = {This study demonstrates the influence of the functionalization method (Mechanical Mixture -MM- and Dual Function Materials -DFM-) of two CO2 adsorbent species (Na and Ca) in a catalytic fixed-bed reactor for CO2 methanation. The experiments consisted of cycles beginning with a CO2 adsorption stage followed by a methanation stage (with H2), interspersed with or without inert purge periods. The greatest enhancement in methane generation was observed in experiments with a mechanical mixture (MM) of NiFe/γ-Al2O3 catalyst and Na2O/γ-Al2O3. The methane production capacity was tested over a temperature range comprised between 200 and 400 °C, with values over 380 μmol/g obtained under moderate conditions (350 °C and pCO2 = 0.12 bar) and selectivity to methane close to 100 %. Since the ultimate goal is the methanation of the CO2 present in a biogas (without removing CH4), the potential effect of the presence of methane during the CO2 adsorption stages was also investigated. To achieve this task, a feed stream representative of a sweetened biogas coming from the anaerobic decomposition of municipal solid waste (MSW) (70 %v CH4 and 30 %v CO2) was used. The results showed no adverse effects along the successive cycles, paving the way to the use of these solids for biogas upgrading. On the other hand, the catalyst did not show a significant loss of activity after several hours of repetitive adsorption-methanation cycles.},
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This study demonstrates the influence of the functionalization method (Mechanical Mixture -MM- and Dual Function Materials -DFM-) of two CO2 adsorbent species (Na and Ca) in a catalytic fixed-bed reactor for CO2 methanation. The experiments consisted of cycles beginning with a CO2 adsorption stage followed by a methanation stage (with H2), interspersed with or without inert purge periods. The greatest enhancement in methane generation was observed in experiments with a mechanical mixture (MM) of NiFe/γ-Al2O3 catalyst and Na2O/γ-Al2O3. The methane production capacity was tested over a temperature range comprised between 200 and 400 °C, with values over 380 μmol/g obtained under moderate conditions (350 °C and pCO2 = 0.12 bar) and selectivity to methane close to 100 %. Since the ultimate goal is the methanation of the CO2 present in a biogas (without removing CH4), the potential effect of the presence of methane during the CO2 adsorption stages was also investigated. To achieve this task, a feed stream representative of a sweetened biogas coming from the anaerobic decomposition of municipal solid waste (MSW) (70 %v CH4 and 30 %v CO2) was used. The results showed no adverse effects along the successive cycles, paving the way to the use of these solids for biogas upgrading. On the other hand, the catalyst did not show a significant loss of activity after several hours of repetitive adsorption-methanation cycles.
González-Pizarro, R.; Calero-Berrocal, R.; Lasobras, J.; Renda, S.; Rodríguez-Pardo, M. R.; Soler, J.; Menéndez, M.; Herguido, J.
Tuning e-fuel selectivity in sorption-enhanced CO2 hydrogenation over In2O3/ZrO2: The effect of LTA and FAU zeolites Journal Article
En: Fuel, vol. 406, pp. 136974, 2026, ISSN: 0016-2361.
@article{GONZALEZPIZARRO2026136974,
title = {Tuning e-fuel selectivity in sorption-enhanced CO2 hydrogenation over In2O3/ZrO2: The effect of LTA and FAU zeolites},
author = {R. González-Pizarro and R. Calero-Berrocal and J. Lasobras and S. Renda and M. R. Rodríguez-Pardo and J. Soler and M. Menéndez and J. Herguido},
url = {https://www.sciencedirect.com/science/article/pii/S0016236125026997},
doi = {https://doi.org/10.1016/j.fuel.2025.136974},
issn = {0016-2361},
year = {2026},
date = {2026-01-01},
journal = {Fuel},
volume = {406},
pages = {136974},
abstract = {The e-fuels synthesis via CO2 hydrogenation and the Sorption Enhanced Reaction technology are captivating strategies for CO2 utilization and the integration of renewable energy sources. This study focuses on enhancing the conversion of CO2 over an In2O3/ZrO2 catalyst by incorporating LTA zeolites (3A and 4A) and a FAU zeolite (13X). Key operational parameters, such as temperature (T), Gas Hour Space Velocity (GHSV), type of zeolite, and Zeolite: Catalyst mass ratio (Z/C), were systematically varied. LTA zeolites (3A and 4A) provided the highest CO2 conversions. The introduction of a water-adsorbing solid into the reactor significantly altered the products yield and selectivity. While the selectivity towards CH4, CH3OH, and C2H6O appeared to lay on the type of zeolite, the selectivity towards CO remained unaffected. Zeolite 3A demonstrated the greatest enhancement in selectivity towards CH4 and CH3OH, whereas the synthesis of C2H6O was favored by zeolites 4A and 13X. The Zeolite:Catalyst mass ratio also played a crucial role in process performance, influencing both CO2 conversion and product selectivity. Increasing this ratio improved CO2 conversion and reduced CO selectivity under all operating conditions, while CH4 selectivity increased. However, the selectivity toward CH3OH and C2H6O exhibited an anomalous and complementary behavior. While a maximum was observed for DME, a minimum was registered in methanol production, suggesting a dependency of the dehydration reaction kinetics on the amount of water produced during the reaction.},
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The e-fuels synthesis via CO2 hydrogenation and the Sorption Enhanced Reaction technology are captivating strategies for CO2 utilization and the integration of renewable energy sources. This study focuses on enhancing the conversion of CO2 over an In2O3/ZrO2 catalyst by incorporating LTA zeolites (3A and 4A) and a FAU zeolite (13X). Key operational parameters, such as temperature (T), Gas Hour Space Velocity (GHSV), type of zeolite, and Zeolite: Catalyst mass ratio (Z/C), were systematically varied. LTA zeolites (3A and 4A) provided the highest CO2 conversions. The introduction of a water-adsorbing solid into the reactor significantly altered the products yield and selectivity. While the selectivity towards CH4, CH3OH, and C2H6O appeared to lay on the type of zeolite, the selectivity towards CO remained unaffected. Zeolite 3A demonstrated the greatest enhancement in selectivity towards CH4 and CH3OH, whereas the synthesis of C2H6O was favored by zeolites 4A and 13X. The Zeolite:Catalyst mass ratio also played a crucial role in process performance, influencing both CO2 conversion and product selectivity. Increasing this ratio improved CO2 conversion and reduced CO selectivity under all operating conditions, while CH4 selectivity increased. However, the selectivity toward CH3OH and C2H6O exhibited an anomalous and complementary behavior. While a maximum was observed for DME, a minimum was registered in methanol production, suggesting a dependency of the dehydration reaction kinetics on the amount of water produced during the reaction.
Renda, Simona; Soler, Jaime; Menéndez, Miguel; Herguido, Javier
Doped In2O3/ZrO2 catalysts to drive selectivity toward DME in one-pot CO2 hydrogenation Journal Article
En: Applied Catalysis A: General, vol. 710, pp. 120682, 2026, ISSN: 0926-860X.
@article{RENDA2026120682,
title = {Doped In2O3/ZrO2 catalysts to drive selectivity toward DME in one-pot CO2 hydrogenation},
author = {Simona Renda and Jaime Soler and Miguel Menéndez and Javier Herguido},
url = {https://www.sciencedirect.com/science/article/pii/S0926860X25005848},
doi = {https://doi.org/10.1016/j.apcata.2025.120682},
issn = {0926-860X},
year = {2026},
date = {2026-01-01},
journal = {Applied Catalysis A: General},
volume = {710},
pages = {120682},
abstract = {This study investigates single-pass dimethyl ether synthesis at mild pressure conditions using novel bifunctional catalysts based on indium-modified formulations and incorporating Ni, Cu, Pt, and Pd as active metals. Additionally, the substitution of the conventional HZSM-5 zeolite with 4A zeolite as the dehydration component was evaluated. Although 4A zeolite exhibited lower dehydration activity, it contributed to an overall improvement in DME selectivity. The incorporation of secondary metals into the In2O3-ZrO2 formulation reduced catalytic activity but enhanced selectivity, ultimately increasing DME yield. The formation of by-products such as light olefins and methane was significantly dependent on the metal used: Ni, Pt, and Pd reduced olefin production, though Ni promoted excessive methane formation across the whole temperature range. Notably, the Pt-based catalyst completely suppressed by-product formation across the temperature range studied. While the In2O3-ZrO2-based catalysts generally displayed lower space–time yields than the commercial reference, they achieved comparable performance at 280 °C. Due to their superior selectivity, these formulations are promising for developing even better performing catalysts, to be excellent candidates in industrial processes, where the operation with recycle loops requires a high product purity.},
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This study investigates single-pass dimethyl ether synthesis at mild pressure conditions using novel bifunctional catalysts based on indium-modified formulations and incorporating Ni, Cu, Pt, and Pd as active metals. Additionally, the substitution of the conventional HZSM-5 zeolite with 4A zeolite as the dehydration component was evaluated. Although 4A zeolite exhibited lower dehydration activity, it contributed to an overall improvement in DME selectivity. The incorporation of secondary metals into the In2O3-ZrO2 formulation reduced catalytic activity but enhanced selectivity, ultimately increasing DME yield. The formation of by-products such as light olefins and methane was significantly dependent on the metal used: Ni, Pt, and Pd reduced olefin production, though Ni promoted excessive methane formation across the whole temperature range. Notably, the Pt-based catalyst completely suppressed by-product formation across the temperature range studied. While the In2O3-ZrO2-based catalysts generally displayed lower space–time yields than the commercial reference, they achieved comparable performance at 280 °C. Due to their superior selectivity, these formulations are promising for developing even better performing catalysts, to be excellent candidates in industrial processes, where the operation with recycle loops requires a high product purity.
González-Pizarro, R.; Renda, S.; Lasobras, J.; Soler, J.; Menéndez, M.; Herguido, J.
Low loading copper-based catalysts for effective CO2 hydrogenation to methanol Journal Article
En: Fuel, vol. 408, pp. 137642, 2026, ISSN: 0016-2361.
@article{GONZALEZPIZARRO2026137642,
title = {Low loading copper-based catalysts for effective CO2 hydrogenation to methanol},
author = {R. González-Pizarro and S. Renda and J. Lasobras and J. Soler and M. Menéndez and J. Herguido},
url = {https://www.sciencedirect.com/science/article/pii/S001623612503368X},
doi = {https://doi.org/10.1016/j.fuel.2025.137642},
issn = {0016-2361},
year = {2026},
date = {2026-01-01},
journal = {Fuel},
volume = {408},
pages = {137642},
abstract = {Methanol synthesis via CO2 hydrogenation is an emerging Power-to-Liquid (PtL) technology aimed to accelerate the energy transition and the defossilization of key sectors, particularly maritime transport. This study focuses on the study of low loading formulations, to minimize the catalyst cost. Key operational variables including temperature (T), Weight Hourly Space Velocity (WHSV), copper and zinc loadings, and aging state were systematically varied. An overall active phase loading of 10 %wt emerged as optimal. Within this total loading, a 5 %wtCu-5 %wtZn/ZrO2 catalysts delivered higher methanol productivity than 10 %wtCu/ZrO2; however, the bimetallic catalysts showed pronounced deactivation under water-rich atmospheres, establishing 10 %wtCu/ZrO2 as the most promising catalysts. Operating temperature and WHSV exerted a strong, synergistic influence on CH3OH formation; in particular, increasing WHSV shifted the reaction away from thermodynamic control and boosted methanol synthesis. Finally, the catalytic performance of these low-loading catalysts was benchmarked against high-copper-loading methanol catalysts reported in the literature by critically compare their activities as a function of the residence time (τ) calculated at reaction conditions. This assessment revealed that the proposed formulation is highly competitive when compared to most conventional formulation, with a maximum methanol space time yield (STYCH3OH) of 3.9 gCH3OH gCu-1 h-1. This comparison confirms that the catalysts proposed in this study could offer a remarkably more efficient use of the active phase than the conventional high-copper-loading catalysts.},
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Methanol synthesis via CO2 hydrogenation is an emerging Power-to-Liquid (PtL) technology aimed to accelerate the energy transition and the defossilization of key sectors, particularly maritime transport. This study focuses on the study of low loading formulations, to minimize the catalyst cost. Key operational variables including temperature (T), Weight Hourly Space Velocity (WHSV), copper and zinc loadings, and aging state were systematically varied. An overall active phase loading of 10 %wt emerged as optimal. Within this total loading, a 5 %wtCu-5 %wtZn/ZrO2 catalysts delivered higher methanol productivity than 10 %wtCu/ZrO2; however, the bimetallic catalysts showed pronounced deactivation under water-rich atmospheres, establishing 10 %wtCu/ZrO2 as the most promising catalysts. Operating temperature and WHSV exerted a strong, synergistic influence on CH3OH formation; in particular, increasing WHSV shifted the reaction away from thermodynamic control and boosted methanol synthesis. Finally, the catalytic performance of these low-loading catalysts was benchmarked against high-copper-loading methanol catalysts reported in the literature by critically compare their activities as a function of the residence time (τ) calculated at reaction conditions. This assessment revealed that the proposed formulation is highly competitive when compared to most conventional formulation, with a maximum methanol space time yield (STYCH3OH) of 3.9 gCH3OH gCu-1 h-1. This comparison confirms that the catalysts proposed in this study could offer a remarkably more efficient use of the active phase than the conventional high-copper-loading catalysts.
González-Pizarro, R.; Lasobras, J.; Renda, S.; Soler, J.; Menéndez, M.; Herguido, J.
En: Separation and Purification Technology, vol. 404, pp. 138902, 2026, ISSN: 1383-5866.
@article{GONZALEZPIZARRO2026138902,
title = {Overcoming thermodynamic limitations of the low-temperature reverse water-gas shift in a sorption-enhanced fluidized bed reactor with continuous sorbent feeding and separation (SEFBR + CSF)},
author = {R. González-Pizarro and J. Lasobras and S. Renda and J. Soler and M. Menéndez and J. Herguido},
url = {https://www.sciencedirect.com/science/article/pii/S1383586626021684},
doi = {https://doi.org/10.1016/j.seppur.2026.138902},
issn = {1383-5866},
year = {2026},
date = {2026-01-01},
journal = {Separation and Purification Technology},
volume = {404},
pages = {138902},
abstract = {Abstract
This work presents a novel approach for intensifying the reverse water gas shift (rWGS) reaction by integrating an advanced fluidized-bed reactor design with a continuous solid sorbent feeding/separation strategy. The proposed Sorption Enhanced Fluidized Bed Reactor combined with Continuous Sorbent Feeding and Separation (SEFBR + CSF) enables continuous operation while maintaining the intensification effect traditionally associated with temporal-limited sorption-enhanced processes. This configuration externalizes the regeneration of the water-adsorbing zeolite, which is continuously and selectively withdrawn from the reactor in a partially or fully saturated state and replaced with regenerated material, thereby sustaining the sorption capacity throughout operation. Process intensification was experimentally demonstrated in the SEFBR + CSF configuration, which achieved CO yields significantly higher than those obtained in the conventional fluidized-bed reactor (cFBR). During the interval in which continuous sorbent feeding was applied, CO production surpassed the thermodynamic equilibrium limit at operating temperatures between 260 and 300 °C. When compared with literature data under similar conditions, the proposed system exhibited superior CO yields, particularly in the low-temperature regime where conventional LT-rWGS performance is typically limited. Overall, the SEFBR + CSF system represents a promising pathway for continuous sorption-enhanced operation, providing improved efficiency and enabling the process to exceed the equilibrium constraints of the LT-rWGS reaction.},
keywords = {},
pubstate = {published},
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Abstract
This work presents a novel approach for intensifying the reverse water gas shift (rWGS) reaction by integrating an advanced fluidized-bed reactor design with a continuous solid sorbent feeding/separation strategy. The proposed Sorption Enhanced Fluidized Bed Reactor combined with Continuous Sorbent Feeding and Separation (SEFBR + CSF) enables continuous operation while maintaining the intensification effect traditionally associated with temporal-limited sorption-enhanced processes. This configuration externalizes the regeneration of the water-adsorbing zeolite, which is continuously and selectively withdrawn from the reactor in a partially or fully saturated state and replaced with regenerated material, thereby sustaining the sorption capacity throughout operation. Process intensification was experimentally demonstrated in the SEFBR + CSF configuration, which achieved CO yields significantly higher than those obtained in the conventional fluidized-bed reactor (cFBR). During the interval in which continuous sorbent feeding was applied, CO production surpassed the thermodynamic equilibrium limit at operating temperatures between 260 and 300 °C. When compared with literature data under similar conditions, the proposed system exhibited superior CO yields, particularly in the low-temperature regime where conventional LT-rWGS performance is typically limited. Overall, the SEFBR + CSF system represents a promising pathway for continuous sorption-enhanced operation, providing improved efficiency and enabling the process to exceed the equilibrium constraints of the LT-rWGS reaction.
This work presents a novel approach for intensifying the reverse water gas shift (rWGS) reaction by integrating an advanced fluidized-bed reactor design with a continuous solid sorbent feeding/separation strategy. The proposed Sorption Enhanced Fluidized Bed Reactor combined with Continuous Sorbent Feeding and Separation (SEFBR + CSF) enables continuous operation while maintaining the intensification effect traditionally associated with temporal-limited sorption-enhanced processes. This configuration externalizes the regeneration of the water-adsorbing zeolite, which is continuously and selectively withdrawn from the reactor in a partially or fully saturated state and replaced with regenerated material, thereby sustaining the sorption capacity throughout operation. Process intensification was experimentally demonstrated in the SEFBR + CSF configuration, which achieved CO yields significantly higher than those obtained in the conventional fluidized-bed reactor (cFBR). During the interval in which continuous sorbent feeding was applied, CO production surpassed the thermodynamic equilibrium limit at operating temperatures between 260 and 300 °C. When compared with literature data under similar conditions, the proposed system exhibited superior CO yields, particularly in the low-temperature regime where conventional LT-rWGS performance is typically limited. Overall, the SEFBR + CSF system represents a promising pathway for continuous sorption-enhanced operation, providing improved efficiency and enabling the process to exceed the equilibrium constraints of the LT-rWGS reaction.
Aragüés-Aldea, P.; Durán, P.; Mercader, V. D.; Renda, S.; Francés, E.; Peña, J. A.; Herguido, J.
Packed-bed membrane reactors as a strategy for selective CO2 methanation Journal Article
En: Catalysis Today, vol. 476, pp. 115899, 2026, ISSN: 0920-5861.
@article{ARAGUESALDEA2026115899,
title = {Packed-bed membrane reactors as a strategy for selective CO2 methanation},
author = {P. Aragüés-Aldea and P. Durán and V. D. Mercader and S. Renda and E. Francés and J. A. Peña and J. Herguido},
url = {https://www.sciencedirect.com/science/article/pii/S0920586126002233},
doi = {https://doi.org/10.1016/j.cattod.2026.115899},
issn = {0920-5861},
year = {2026},
date = {2026-01-01},
journal = {Catalysis Today},
volume = {476},
pages = {115899},
abstract = {CO2 methanation represents a key route within Power-to-X strategies for converting captured carbon into synthetic natural gas. However, its efficiency is limited by thermodynamic constraints, heat management issues, and undesired CO formation due to the reverse water–gas shift reaction. In this work, a novel packed-bed membrane reactor (PBMR), conceived as an evolution of the polytropic packed-bed reactor (PPBR), is proposed and experimentally validated for selective CO2 methanation. The reactor enables distributed reactant feeding through a porous membrane wall, allowing enhanced control over local reaction environments along the catalytic bed. A Ni–Fe/Al2O3 catalyst was employed and tested under various operating conditions, including different weight hourly space velocities (WHSV) and feeding configurations (conventional, co-current, and counter-current). The influence of distributing either H2 or CO2 was systematically investigated in terms of CO2 conversion, temperature profiles, and CO selectivity. While distributed configurations did not improve overall CO2 conversion compared to conventional operation, they significantly affected selectivity. In particular, CO2-distributed feeding consistently reduced CO selectivity under iso-conversion conditions, achieving up to a 40% decrease in the most favorable case. This significant reduction highlights the effectiveness of spatial reactant management in driving the reaction pathway toward methane. Overall, these results underline the critical role of reactor design in overcoming selectivity limitations and demonstrate the potential of membrane-assisted distributed feeding as a process intensification strategy for CO2 methanation.},
keywords = {},
pubstate = {published},
tppubtype = {article}
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CO2 methanation represents a key route within Power-to-X strategies for converting captured carbon into synthetic natural gas. However, its efficiency is limited by thermodynamic constraints, heat management issues, and undesired CO formation due to the reverse water–gas shift reaction. In this work, a novel packed-bed membrane reactor (PBMR), conceived as an evolution of the polytropic packed-bed reactor (PPBR), is proposed and experimentally validated for selective CO2 methanation. The reactor enables distributed reactant feeding through a porous membrane wall, allowing enhanced control over local reaction environments along the catalytic bed. A Ni–Fe/Al2O3 catalyst was employed and tested under various operating conditions, including different weight hourly space velocities (WHSV) and feeding configurations (conventional, co-current, and counter-current). The influence of distributing either H2 or CO2 was systematically investigated in terms of CO2 conversion, temperature profiles, and CO selectivity. While distributed configurations did not improve overall CO2 conversion compared to conventional operation, they significantly affected selectivity. In particular, CO2-distributed feeding consistently reduced CO selectivity under iso-conversion conditions, achieving up to a 40% decrease in the most favorable case. This significant reduction highlights the effectiveness of spatial reactant management in driving the reaction pathway toward methane. Overall, these results underline the critical role of reactor design in overcoming selectivity limitations and demonstrate the potential of membrane-assisted distributed feeding as a process intensification strategy for CO2 methanation.
Proceedings
Becerril Ferrer, Miguel Angel; Mercader Plou, Victor Daniel; Durán Sánchez, Paúl; Francés Pérez, Eva; Herguido, Javier; Peña Llorente, José Ángel
vol. 14, 2026.
@proceedings{BecerrilFerrer_MercaderPlou_DuránSánchez_FrancésPérez_Herguido_PeñaLlorente_2026,
title = {Influence of operating pressure and H2S presence on the stability and performance of commercial catalysts for CO2 methanation},
author = {Becerril Ferrer, Miguel Angel and Mercader Plou, Victor Daniel and Durán Sánchez, Paúl and Francés Pérez, Eva and Herguido, Javier and Peña Llorente, José Ángel},
url = {https://papiro.unizar.es/ojs/index.php/jji3a/article/view/13366},
doi = {10.26754/jji-i3a.202613366},
year = {2026},
date = {2026-07-01},
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Aragüés-Aldea, Pablo; López, Natalia; Durán, Paúl; Mercader, Víctor Daniel; Francés, Eva; Peña, José Ángel; Herguido, Javier
Intensification of biogas upgrading through side distribution in a Packed Bed Membrane Reactor (PBMR) Proceedings
vol. 14, 2026.
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title = {Intensification of biogas upgrading through side distribution in a Packed Bed Membrane Reactor (PBMR)},
author = {Pablo Aragüés-Aldea and López, Natalia and Durán, Paúl and Mercader, Víctor Daniel and Francés, Eva and Peña, José Ángel and Herguido, Javier},
url = {https://papiro.unizar.es/ojs/index.php/jji3a/article/view/13261},
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year = {2026},
date = {2026-07-01},
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González Pizarro, Rodrigo; Renda, Simona; Lasobras Laguna, Javier; Soler Herrero, Jaime; Menéndez Sastre, Miguel; Herguido Huerta, Javier
Intensified Catalytic CO₂ Conversion into e-Fuels: A Study of Different Process Intensification Strategies Proceedings
vol. 14, 2026.
@proceedings{GonzálezPizarro_Renda_LasobrasLaguna_SolerHerrero_MenéndezSastre_HerguidoHuerta_2026,
title = {Intensified Catalytic CO₂ Conversion into e-Fuels: A Study of Different Process Intensification Strategies},
author = {González Pizarro, Rodrigo and Renda, Simona and Lasobras Laguna, Javier and Soler Herrero, Jaime and Menéndez Sastre, Miguel and Herguido Huerta, Javier},
url = {https://papiro.unizar.es/ojs/index.php/jji3a/article/view/13351},
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Soria Romeo, Jorge; Durán Sánchez, Paúl; Lacasta Miguel, Javier
Machine Learning-Based System for Matrix Effect Correction in Gas Chromatography Proceedings
vol. 14, 2026.
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title = {Machine Learning-Based System for Matrix Effect Correction in Gas Chromatography},
author = {Soria Romeo, Jorge and Durán Sánchez, Paúl and Lacasta Miguel, Javier},
url = {https://papiro.unizar.es/ojs/index.php/jji3a/article/view/13324},
doi = {10.26754/jji-i3a.202613324},
year = {2026},
date = {2026-07-01},
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Flores Calvo, Diego; González Pizarro, Rodrigo; Soler Herrero, Jaime; Menéndez Sastre, Miguel; Renda, Simona; Lasobras Laguna, Javier; Herguido Huerta, Javier
vol. 14, 2026.
@proceedings{FloresCalvo_GonzálezPizarro_SolerHerrero_MenéndezSastre_Renda_LasobrasLaguna_HerguidoHuerta_2026,
title = {Optimización de las condiciones de operación para la síntesis de metanol vía hidrogenación catalítica de CO2 en reactor de lecho fijo},
author = {Flores Calvo, Diego and González Pizarro, Rodrigo and Soler Herrero, Jaime and Menéndez Sastre, Miguel and Renda, Simona and Lasobras Laguna, Javier and Herguido Huerta, Javier},
url = {https://papiro.unizar.es/ojs/index.php/jji3a/article/view/13387},
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year = {2026},
date = {2026-07-01},
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Oliver Marco, Melania; Herguido, Javier; Peña, José Ángel; Durán, Paul; Mercader Plou, Víctor Daniel; Francés, Eva
Process intensification of the Sabatier reaction for CO2 methanation with 13X zeolite Proceedings
vol. 14, 2026.
@proceedings{OliverMarco_Herguido_Peña_Durán_MercaderPlou_Francés_2026,
title = {Process intensification of the Sabatier reaction for CO2 methanation with 13X zeolite},
author = {Oliver Marco, Melania and Herguido, Javier and Peña, José Ángel and Durán, Paul and Mercader Plou, Víctor Daniel and Francés, Eva},
url = {https://papiro.unizar.es/ojs/index.php/jji3a/article/view/13365},
doi = {10.26754/jji-i3a.202613365},
year = {2026},
date = {2026-07-01},
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Uriel, Olga; Mercader Plou, Víctor; Durán Sánchez, Paúl; Francés Pérez, Eva; Peña Llorente, José Ángel; Herguido, Javier
vol. 14, 2026.
@proceedings{Uriel_MercaderPlou_DuránSánchez_FrancésPérez_PeñaLlorente_Herguido_2026,
title = {From Biogas to SNG in a Fixed Bed Reactor by Alternating Adsorption/Methanation Stages with Multifunctional Solids},
author = {Uriel, Olga and Mercader Plou, Víctor and Durán Sánchez, Paúl and Francés Pérez, Eva and Peña Llorente, José Ángel and Herguido, Javier},
url = {https://papiro.unizar.es/ojs/index.php/jji3a/article/view/13368},
doi = {10.26754/jji-i3a.202613368},
year = {2026},
date = {2026-07-01},
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journal = {Jornada de Jóvenes Investigadores del I3A},
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Uriel, Olga; Mercader Plou, Víctor; Durán Sánchez, Paúl; Francés Pérez, Eva; Peña Llorente, José Ángel; Herguido, Javier
vol. 14, 2026.
@proceedings{Uriel_MercaderPlou_DuránSánchez_FrancésPérez_PeñaLlorente_Herguido_2026b,
title = {From Biogas to SNG in a Fixed Bed Reactor by Alternating Adsorption/Methanation Stages with Multifunctional Solids},
author = {Uriel, Olga and Mercader Plou, Víctor and Durán Sánchez, Paúl and Francés Pérez, Eva and Peña Llorente, José Ángel and Herguido, Javier},
url = {https://papiro.unizar.es/ojs/index.php/jji3a/article/view/13368},
doi = {10.26754/jji-i3a.202613368},
year = {2026},
date = {2026-07-01},
urldate = {2026-07-01},
journal = {Jornada de Jóvenes Investigadores del I3A},
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2025
Journal Articles
Aragüés-Aldea, P.; Mercader, V. D.; Durán, P.; Francés, E.; Peña, J. Á.; Herguido, J.
Biogas upgrading through CO2 methanation in a multiple-inlet fixed bed reactor: Simulated parametric analysis Journal Article
En: Journal of CO2 Utilization, vol. 93, pp. 103038, 2025, ISSN: 2212-9820.
@article{ARAGUESALDEA2025103038,
title = {Biogas upgrading through CO2 methanation in a multiple-inlet fixed bed reactor: Simulated parametric analysis},
author = {P. Aragüés-Aldea and V. D. Mercader and P. Durán and E. Francés and J. Á. Peña and J. Herguido},
url = {https://www.sciencedirect.com/science/article/pii/S2212982025000228},
doi = {https://doi.org/10.1016/j.jcou.2025.103038},
issn = {2212-9820},
year = {2025},
date = {2025-01-01},
journal = {Journal of CO2 Utilization},
volume = {93},
pages = {103038},
abstract = {A simulation of the catalytic CO2 methanation reaction was carried out, evaluating the effect of reactants distributed feeding throughout the bed. The main operational parameters were studied in a multiple-inlet reactor to test their effect on conversions and, most importantly, on selectivities towards both CO and CH4 as reaction products. The analyzed parameters were, firstly, the number of feeding points (N) and the dosage degree of reactants, followed by temperature (T), partial pressures of reactants (H2:CO2 ratios), and the composition of a sweetened biogas as feeding stream (CH4:CO2 ratios). It is confirmed that a distribution of biogas through several side inlets improves selectivities to the desired CH4 product, over other feeding configurations. The effect of distributing reactants becomes intensified when the number of lateral feedings increases. This observation supports the experimental trends already proven in previous works. Regarding main operation parameters such as temperature and H2:CO2 molar ratio, the analysis confirmed that their influence on selectivities acts just as predicted at low conversions. However, when these conversions become higher the space velocity (WHSV) is the most important factor for selectivities. Finally, no significant changes in reaction performance were obtained when modifying the biogas CH4:CO2 ratio in the broad range of methane concentrations from 55 v% to 70 v%.},
keywords = {},
pubstate = {published},
tppubtype = {article}
}
A simulation of the catalytic CO2 methanation reaction was carried out, evaluating the effect of reactants distributed feeding throughout the bed. The main operational parameters were studied in a multiple-inlet reactor to test their effect on conversions and, most importantly, on selectivities towards both CO and CH4 as reaction products. The analyzed parameters were, firstly, the number of feeding points (N) and the dosage degree of reactants, followed by temperature (T), partial pressures of reactants (H2:CO2 ratios), and the composition of a sweetened biogas as feeding stream (CH4:CO2 ratios). It is confirmed that a distribution of biogas through several side inlets improves selectivities to the desired CH4 product, over other feeding configurations. The effect of distributing reactants becomes intensified when the number of lateral feedings increases. This observation supports the experimental trends already proven in previous works. Regarding main operation parameters such as temperature and H2:CO2 molar ratio, the analysis confirmed that their influence on selectivities acts just as predicted at low conversions. However, when these conversions become higher the space velocity (WHSV) is the most important factor for selectivities. Finally, no significant changes in reaction performance were obtained when modifying the biogas CH4:CO2 ratio in the broad range of methane concentrations from 55 v% to 70 v%.
Renda, Simona; Soler, Jaime; Herguido, Javier; Menéndez, Miguel
En: Biomass and Bioenergy, vol. 197, pp. 107764, 2025, ISSN: 0961-9534.
@article{RENDA2025107764,
title = {Effect of particles size and density on the segregation of catalyst-sorbent mixtures for direct sorption-enhanced DME synthesis: Experimental and mathematical study},
author = {Simona Renda and Jaime Soler and Javier Herguido and Miguel Menéndez},
url = {https://www.sciencedirect.com/science/article/pii/S0961953425001758},
doi = {https://doi.org/10.1016/j.biombioe.2025.107764},
issn = {0961-9534},
year = {2025},
date = {2025-01-01},
journal = {Biomass and Bioenergy},
volume = {197},
pages = {107764},
abstract = {Direct sorption-enhanced dimethyl ether synthesis (SEDMES) is a promising process for the production of fuels from CO2 sources. Using novel technologies, the process can be run exploiting the phenomena of particles segregation in a fluidized bed reactor. However, the knowledge on the solid movement and the segregation patterns is a mandatory preliminary step for the setup of the final application. In this study, we evaluated the impact of particles size and density on the segregation patterns, and we used the Gibilaro and Rowe (GR) model to analytically represent the experimental results. It was observed that the variation of both parameters influences segregation, even though a higher separation degree in a wider operating velocity range was observed when a higher density ratio was induced between the two solids. Through the experimental analysis, five possible bed configurations were identified, and a consideration was made on the aims of the GR model to adjust the mathematical representation to the present case. By considering the bottom portion of the bed as a jetsam-rich phase and not – as previously reported – as a segregated layer, a mass balance on the catalyst allowed to obtain a faithful analytical representation of the experimental segregation patterns.},
keywords = {},
pubstate = {published},
tppubtype = {article}
}
Direct sorption-enhanced dimethyl ether synthesis (SEDMES) is a promising process for the production of fuels from CO2 sources. Using novel technologies, the process can be run exploiting the phenomena of particles segregation in a fluidized bed reactor. However, the knowledge on the solid movement and the segregation patterns is a mandatory preliminary step for the setup of the final application. In this study, we evaluated the impact of particles size and density on the segregation patterns, and we used the Gibilaro and Rowe (GR) model to analytically represent the experimental results. It was observed that the variation of both parameters influences segregation, even though a higher separation degree in a wider operating velocity range was observed when a higher density ratio was induced between the two solids. Through the experimental analysis, five possible bed configurations were identified, and a consideration was made on the aims of the GR model to adjust the mathematical representation to the present case. By considering the bottom portion of the bed as a jetsam-rich phase and not – as previously reported – as a segregated layer, a mass balance on the catalyst allowed to obtain a faithful analytical representation of the experimental segregation patterns.
Mercader, V. D.; Aragüés-Aldea, P.; Durán, P.; Francés, E.; Herguido, J.; Peña, J. A.
Optimizing Sorption Enhanced Methanation (SEM) of CO2 with Ni3Fe + LTA 5 A mixtures Journal Article
En: Catalysis Today, vol. 453, pp. 115262, 2025, ISSN: 0920-5861.
@article{MERCADER2025115262,
title = {Optimizing Sorption Enhanced Methanation (SEM) of CO2 with Ni3Fe + LTA 5 A mixtures},
author = {V. D. Mercader and P. Aragüés-Aldea and P. Durán and E. Francés and J. Herguido and J. A. Peña},
url = {https://www.sciencedirect.com/science/article/pii/S092058612500080X},
doi = {https://doi.org/10.1016/j.cattod.2025.115262},
issn = {0920-5861},
year = {2025},
date = {2025-01-01},
journal = {Catalysis Today},
volume = {453},
pages = {115262},
abstract = {This study investigates the integration of catalytic CO2 methanation and water adsorption using a Ni-Fe-based catalyst and LTA 5 A zeolite to enhance methane production via the Sabatier reaction. By mitigating thermodynamic limitations through in situ water removal, the research explores key operational parameters, including temperature, space velocity, and H₂:CO₂ feed ratios, to optimize process performance. The findings highlight that a temperature of 300 °C, a WHSV of 1.50 × 104 (STP) mL·gcat−1·h−1 (4.86 gCO2·gcat⁻¹·h⁻¹), and a H₂:CO₂ molar ratio equal to 5:1, result in enhanced methane yields, shifting thermodynamic equilibrium due to water sorption during initial stages. The presence of methane in the feed, representative of a biogas, demonstrated negligible effects on methane yields under optimal conditions, underscoring the method’s feasibility for direct biogas upgrading. While the process achieved significant intensification, challenges such as loss of activity of the bed of solids (catalyst plus water adsorbent) were identified, necessitating further advancements in both catalyst and adsorbent stability, as well as a deeper study on their interaction. The study provides a pathway for scaling up adsorption-enhanced methanation technologies to achieve renewable methane production, addressing the dual goals of carbon management and energy storage.},
keywords = {},
pubstate = {published},
tppubtype = {article}
}
This study investigates the integration of catalytic CO2 methanation and water adsorption using a Ni-Fe-based catalyst and LTA 5 A zeolite to enhance methane production via the Sabatier reaction. By mitigating thermodynamic limitations through in situ water removal, the research explores key operational parameters, including temperature, space velocity, and H₂:CO₂ feed ratios, to optimize process performance. The findings highlight that a temperature of 300 °C, a WHSV of 1.50 × 104 (STP) mL·gcat−1·h−1 (4.86 gCO2·gcat⁻¹·h⁻¹), and a H₂:CO₂ molar ratio equal to 5:1, result in enhanced methane yields, shifting thermodynamic equilibrium due to water sorption during initial stages. The presence of methane in the feed, representative of a biogas, demonstrated negligible effects on methane yields under optimal conditions, underscoring the method’s feasibility for direct biogas upgrading. While the process achieved significant intensification, challenges such as loss of activity of the bed of solids (catalyst plus water adsorbent) were identified, necessitating further advancements in both catalyst and adsorbent stability, as well as a deeper study on their interaction. The study provides a pathway for scaling up adsorption-enhanced methanation technologies to achieve renewable methane production, addressing the dual goals of carbon management and energy storage.
Sanz-Monreal, P.; Mercader, V. D.; Aragüés-Aldea, P.; Durán, P.; Francés, E.; Herguido, J.; Peña, J. A.
Techno-economic assessment of a plant for the upgrading of MSW biogas to synthetic natural gas by thermocatalytic methanation Journal Article
En: Biomass and Bioenergy, vol. 198, pp. 107871, 2025, ISSN: 0961-9534.
@article{SANZMONREAL2025107871,
title = {Techno-economic assessment of a plant for the upgrading of MSW biogas to synthetic natural gas by thermocatalytic methanation},
author = {P. Sanz-Monreal and V. D. Mercader and P. Aragüés-Aldea and P. Durán and E. Francés and J. Herguido and J. A. Peña},
url = {https://www.sciencedirect.com/science/article/pii/S096195342500282X},
doi = {https://doi.org/10.1016/j.biombioe.2025.107871},
issn = {0961-9534},
year = {2025},
date = {2025-01-01},
journal = {Biomass and Bioenergy},
volume = {198},
pages = {107871},
abstract = {This study evaluates the techno-economic feasibility of a plant designed to produce synthetic natural gas (SNG) from biogas through direct catalytic methanation. The proposed facility is simulated with Aspen Plus® v14, using a comprehensive approach that covers the entire process, from biogas pretreatment to the production of the final product. The installation aims to contribute to the development of Power-to-Gas (Power-to-Methane) strategy for decarbonization. The plant, to be located in northeastern Spain, operates at an industrial scale with a production capacity of approximately 1100 Nm3/h of SNG, obtained from a 1425 Nm3/h biogas plant. The process includes five main stages to meet Spanish gas quality standards for grid injection: desulfurization, using amines for sulfur removal; electrolysis, for the generation of renewable hydrogen; thermocatalytic methanation, which combines CO2 from the biogas with hydrogen to enrich the methane content; dehydration, to meet SNG moisture specifications; and cogeneration, intended for the joint production of electricity and steam to meet the plant's energy demands. A detailed analysis of investment costs (CAPEX) and operational expenses (OPEX) is conducted, identifying the key factors influencing the project's profitability. The economic assessment indicates a total capital investment of 21.83 M€ and operational expenses nearly 8 M€ annually. The profitability threshold for the base scenario is estimated at 91.75 €/MWh, exceeding the 2023 natural gas market average in the Iberic peninsula (39.11 €/MWh), highlighting the current economic challenges of SNG production.},
keywords = {},
pubstate = {published},
tppubtype = {article}
}
This study evaluates the techno-economic feasibility of a plant designed to produce synthetic natural gas (SNG) from biogas through direct catalytic methanation. The proposed facility is simulated with Aspen Plus® v14, using a comprehensive approach that covers the entire process, from biogas pretreatment to the production of the final product. The installation aims to contribute to the development of Power-to-Gas (Power-to-Methane) strategy for decarbonization. The plant, to be located in northeastern Spain, operates at an industrial scale with a production capacity of approximately 1100 Nm3/h of SNG, obtained from a 1425 Nm3/h biogas plant. The process includes five main stages to meet Spanish gas quality standards for grid injection: desulfurization, using amines for sulfur removal; electrolysis, for the generation of renewable hydrogen; thermocatalytic methanation, which combines CO2 from the biogas with hydrogen to enrich the methane content; dehydration, to meet SNG moisture specifications; and cogeneration, intended for the joint production of electricity and steam to meet the plant’s energy demands. A detailed analysis of investment costs (CAPEX) and operational expenses (OPEX) is conducted, identifying the key factors influencing the project’s profitability. The economic assessment indicates a total capital investment of 21.83 M€ and operational expenses nearly 8 M€ annually. The profitability threshold for the base scenario is estimated at 91.75 €/MWh, exceeding the 2023 natural gas market average in the Iberic peninsula (39.11 €/MWh), highlighting the current economic challenges of SNG production.
Aragüés-Aldea, P.; Pizarro, R. G.; Durán, P.; Mercader, V. D.; Francés, E.; Peña, J. A.; Herguido, J.
Catalytic CO2 methanation for biogas upgrading using a polytropic fixed bed reactor Journal Article
En: Catalysis Today, vol. 457, pp. 115351, 2025, ISSN: 0920-5861.
@article{ARAGUESALDEA2025115351,
title = {Catalytic CO2 methanation for biogas upgrading using a polytropic fixed bed reactor},
author = {P. Aragüés-Aldea and R. G. Pizarro and P. Durán and V. D. Mercader and E. Francés and J. A. Peña and J. Herguido},
url = {https://www.sciencedirect.com/science/article/pii/S0920586125001695},
doi = {https://doi.org/10.1016/j.cattod.2025.115351},
issn = {0920-5861},
year = {2025},
date = {2025-01-01},
journal = {Catalysis Today},
volume = {457},
pages = {115351},
abstract = {The experiments of this study aim to determine the effect of distributed feeding of reactants throughout the many inlets of a polytropic fixed bed reactor. The effect of dosing either carbon dioxide or hydrogen, was analyzed on the Sabatier reaction (i.e., carbon dioxide methanation) using a Ni-Mn catalyst to carry out the biogas upgrading process. This work analyzes the influence of three feeding configurations (a conventional fixed bed, one with side distribution of biogas, and another with side distribution of hydrogen) and temperatures (350, 375, and 400 °C) for a wide gas hourly space velocity (GHSV) range from 30 × 103 (STP) mL gcat−1 h−1 to more than 200 × 103 (STP) mL gcat−1 h−1. The molar ratios of reactants were always kept constant (H2:CH4:CO2 = 12:7:3) simulating the hydrogenation of the CO2 present in a biogas with a proportion of 70 v% of CH4 and 30 v% of CO2. The empirical results highlight that side distribution of biogas yields improved results over those obtained in a conventional fixed bed reactor, or the one with side distribution of hydrogen. At temperatures of 375 and 400 °C, this feeding configuration brings higher conversions than the other two, while consistently shows greater selectivities to methane for all the conditions tested. As such, its optimal condition to conduct the process is extended to methane space-time yields (STY), for which the highest methane productions are obtained. In addition, the influence of contact time, or GHSV, was determined to be critical both on selectivities and flowrates of methane. It is shown that for a given conversion value, keeping constant all the other parameters, a longer contact time and lower temperature result in an improvement of selectivities to methane. On the other hand, it also affects STY values, where an optimum between the employed flows of reactants and reaction performances is reached at a value of 180 × 103 (STP) mL gcat−1 h−1, independently of experimental conditions.},
keywords = {},
pubstate = {published},
tppubtype = {article}
}
The experiments of this study aim to determine the effect of distributed feeding of reactants throughout the many inlets of a polytropic fixed bed reactor. The effect of dosing either carbon dioxide or hydrogen, was analyzed on the Sabatier reaction (i.e., carbon dioxide methanation) using a Ni-Mn catalyst to carry out the biogas upgrading process. This work analyzes the influence of three feeding configurations (a conventional fixed bed, one with side distribution of biogas, and another with side distribution of hydrogen) and temperatures (350, 375, and 400 °C) for a wide gas hourly space velocity (GHSV) range from 30 × 103 (STP) mL gcat−1 h−1 to more than 200 × 103 (STP) mL gcat−1 h−1. The molar ratios of reactants were always kept constant (H2:CH4:CO2 = 12:7:3) simulating the hydrogenation of the CO2 present in a biogas with a proportion of 70 v% of CH4 and 30 v% of CO2. The empirical results highlight that side distribution of biogas yields improved results over those obtained in a conventional fixed bed reactor, or the one with side distribution of hydrogen. At temperatures of 375 and 400 °C, this feeding configuration brings higher conversions than the other two, while consistently shows greater selectivities to methane for all the conditions tested. As such, its optimal condition to conduct the process is extended to methane space-time yields (STY), for which the highest methane productions are obtained. In addition, the influence of contact time, or GHSV, was determined to be critical both on selectivities and flowrates of methane. It is shown that for a given conversion value, keeping constant all the other parameters, a longer contact time and lower temperature result in an improvement of selectivities to methane. On the other hand, it also affects STY values, where an optimum between the employed flows of reactants and reaction performances is reached at a value of 180 × 103 (STP) mL gcat−1 h−1, independently of experimental conditions.
Renda, Simona; Menéndez, Miguel
Process Intensification for CO2 Hydrogenation to Liquid Fuels Journal Article
En: Catalysts, vol. 15, no. 6, 2025, ISSN: 2073-4344.
@article{catal15060509,
title = {Process Intensification for CO2 Hydrogenation to Liquid Fuels},
author = {Simona Renda and Miguel Menéndez},
url = {https://www.mdpi.com/2073-4344/15/6/509},
doi = {10.3390/catal15060509},
issn = {2073-4344},
year = {2025},
date = {2025-01-01},
journal = {Catalysts},
volume = {15},
number = {6},
abstract = {Liquid fuels obtained from CO2 and green hydrogen (i.e., e-fuels) are powerful tools for decarbonizing economy. Improvements provided by Process Intensification in the existing conventional reactors aim to decrease energy consumption, increase yield, and ensure more compact and safe processes. This review describes the advances in the production of methanol, dimethyl ether, and hydrocarbons by Fischer–Tropsch using different Process Intensification tools, mainly membrane reactors, sorption-enhanced reactors, and structured reactors. Due to the environmental interest, this review article focused on discussing methanol and dimethyl ether synthesis from CO2 + H2, which also represented the most innovative approach. The use of syngas (CO + H2) is generally preferred for the Fischer–Tropsch process; hence, studies examining this process were included in the present review. Both mathematical models and experimental results are discussed. Achievements in the improvement of catalytic reactor performance are described. Experimental results in membrane reactors show increased performance in e-fuels production compared to the conventional packed bed reactor. The combination of sorption and reaction also increases the single-pass conversion and yield, although this improvement is limited by the saturation capacity of the sorbent in most cases.},
keywords = {},
pubstate = {published},
tppubtype = {article}
}
Liquid fuels obtained from CO2 and green hydrogen (i.e., e-fuels) are powerful tools for decarbonizing economy. Improvements provided by Process Intensification in the existing conventional reactors aim to decrease energy consumption, increase yield, and ensure more compact and safe processes. This review describes the advances in the production of methanol, dimethyl ether, and hydrocarbons by Fischer–Tropsch using different Process Intensification tools, mainly membrane reactors, sorption-enhanced reactors, and structured reactors. Due to the environmental interest, this review article focused on discussing methanol and dimethyl ether synthesis from CO2 + H2, which also represented the most innovative approach. The use of syngas (CO + H2) is generally preferred for the Fischer–Tropsch process; hence, studies examining this process were included in the present review. Both mathematical models and experimental results are discussed. Achievements in the improvement of catalytic reactor performance are described. Experimental results in membrane reactors show increased performance in e-fuels production compared to the conventional packed bed reactor. The combination of sorption and reaction also increases the single-pass conversion and yield, although this improvement is limited by the saturation capacity of the sorbent in most cases.