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Artículo científico (JournalArticle). 2023

On the reduction of NiFe/Al2O3 oxygen carrier in high-pressure chemical looping applications

DIGITAL.CSIC. Repositorio Institucional del CSIC
  • Palone, Orlando
  • Ramezani, Rouzbeh
  • Navarro Lahuerta, Claudia
  • Di Felice, Luca
  • Borello, Domenico
  • Grasa Adiego, Gemma
  • Gallucci, Fausto
15 figures., Chemical looping represents a promising technology with various applications ranging from clean power production to alternative syngas production. In this work, two oxygen carriers with different Ni loadings (4.3% wt. and 12% wt.) and similar Fe loadings (9.9% wt. and 8.5% wt.) are synthesized through a co-precipitation/impregnation route and tested in two thermogravimetric analyzers. Firstly, the effect of temperature (700–900 °C) on the oxygen transport capacity and reduction conversion of both materials is assessed at ambient pressure (0.5 nl/min with 20% H2/N2). The influence of material loading is also studied, and it is shown that higher Ni loadings provide a significant improvement in material activity. A complete reduction conversion is achieved at 900 °C and ambient pressure. At high pressure (10–20 bar), tests are carried out in a temperature range of 700–850 °C. The effect of flow rate (2 nl/min to 6 nl/min with 50% H2/N2) is first assessed to prevent external mass transfer limitations. Higher total pressures have a negative effect on reduction kinetics, while higher Ni loadings demonstrate increased final reduction conversion also at high pressure, reaching about 75% conversion after 20 min. The long-term cyclability of the material is also investigated both at low (100 cycles) and high pressure (80 cycles) conditions and a conversion gain is observed throughout the cycles in both cases. No changes in the material microstructure are observed after 80 high-pressure cycles., This project has received funding from the European Union’s Horizon 2020 Research and Innovation Program under grant agreement No 884197 (GLAMOUR)., Peer reviewed
Proyecto: EC/H2020/884197




Artículo científico (JournalArticle). 2023

Catalizadores bimetálicos de Fe y Ni para Chemical Looping Reforming de glicerol

DIGITAL.CSIC. Repositorio Institucional del CSIC
  • Navarro Lahuerta, Claudia
  • Grasa Adiego, Gemma
2 figuras.-- Abstract del póster de Tecnologías para la generación sostenible de energía presentada en la XVI Reunión del Grupo Español del Carbón (Reunión GEC 2023), celebrada en Gijón del 22 al 25 de octubre de 2023., La industria del biodiésel ha experimentado un gran crecimiento en la última década, presentándose como
alternativa a los combustibles fósiles. En su proceso productivo se genera un 10 % en peso de glicerol como
residuo [1]. Esto ha llevado a la búsqueda de alternativas a su purificación, como su uso en procesos de
generación de energía (producción de gas de síntesis o hidrógeno) [2]. En el proyecto H2020 GLAMOUR
se propone el diseño de un proceso de reformado mediante transportadores de oxígeno (Chemical Looping
Reforming, CLR) para producir un gas de síntesis adecuado para un proceso posterior de Fischer Tropsch.
Este proceso, diseñado para operar en reactores de lecho fijo operados de forma dinámica, necesita un
material bi-funcional que actúe como catalizador de reformado y transportador de oxígeno (OC) [3]. Cada
reactor pasará por tres etapas de reacción: oxidación, reducción y reformado. La energía generada durante la
oxidación servirá para mantener las reacciones de reducción y reformado que son endotérmicas equilibrando
el balance energético del proceso.
Tradicionalmente materiales basados en Ni han sido los propuestos en procesos CLR dada su alta actividad
catalítica. Dada la elevada toxicidad del Ni, resulta interesante explorar materiales bimetálicos Fe-Ni que
permiten reducir el contenido de este último.
En este trabajo se evalúa la capacidad de transporte de oxígeno (OTC) y actividad catalítica en condiciones
adecuadas para la producción de gas de síntesis a partir de glicerol en una serie de materiales con diferente
carga de Fe y Ni, así como la estabilidad de estas propiedades al ser sometidos a ciclos., Este trabajo ha recibido financiación del programa de investigación e innovación Horizonte 2020 de la Unión
Europea según el acuerdo de subvención no. 884197 (proyecto GLAMOUR)., Peer reviewed
Proyecto: EC/H2020/884197




Artículo científico (JournalArticle). 2024

Packed-bed chemical looping reforming for renewable syngas production from glycerol with Ni_Fe-based oxygen carriers/catalysts

DIGITAL.CSIC. Repositorio Institucional del CSIC
  • Navarro Lahuerta, Claudia
  • Zaidi, Adam
  • de Leeuwe, Christopher
  • Spallina, Vincenzo
  • Grasa Adiego, Gemma
13 figures, 5 tables., A chemical looping (CL) reactor can provide the energy required to produce syngas from the reforming of glycerol. This can be done through the dynamic operation of packed-bed (PB) reactors that consecutively cycle in a three-stage process that includes oxidation, reduction, and a reforming stage. In this work, Ni-/Fe-based materials were synthesized, characterized, and tested as oxygen carriers and glycerol reforming catalysts during chemical looping reforming in packed-bed (CLR-PB) reactors. Two materials were prepared via coprecipitation/impregnation with different Ni loads (4.3 and 12 wt %) and similar Fe loadings (9.9 and 8.5% wt) and later on granulated to produce particles in a size cut of 0.6–1 mm. The materials presented high catalytic activity in a wide range of reforming temperatures (650–800 °C), being able to achieve over 95% glycerol-to-gas molar conversion in very short gas/solid contact times and at relevant conditions suitable for process scale-up. The results indicated that it is possible to produce materials with a low Ni load, which present sufficient catalytic activity and thermochemical capacity thanks to the presence of Fe, to operate under the glycerol CLR-PB configuration., This project has received funding from the European Union’s Horizon 2020 Research and Innovation Program under grant agreement no. 884197 (GLAMOUR)., Peer reviewed
Proyecto: EC/H2020/884197




Artículo científico (JournalArticle). 2025

Proof-of-concept and model validation of chemical looping reforming of glycerol at relevant conditions

DIGITAL.CSIC. Repositorio Institucional del CSIC
  • Zaidi, Adam
  • de Leeuwe, Christopher
  • Navarro Lahuerta, Claudia
  • McCann, Eimear
  • Wright, Andrew David
  • Grasa Adiego, Gemma
  • Spallina, Vincenzo
14 figures, 4 tables.-- Supplementary information available., Chemical looping reforming (CLR) of glycerol was experimentally and numerically investigated to demonstrate syngas production with integrated in-situ oxygen transfer and heat recovery. A shrinking core model was developed using a Ni-based catalyst, and a 1-dimensional pseudo-homogeneous, axially dispersed plug flow model was validated against laboratory-scale experiments. The packed-bed reactor, containing 500 g of oxygen carrier, showed stable performance over 500 hours with conditions being between 400–900 °C and 1–5 bara. During the air oxidation, a temperature rise of 340 °C of generated from the initial 500 °C. The model achieved excellent agreement with experimental results, using a heat loss coefficient of 46 W·m−2·K-1accurtatly predicting the exothermic oxidation, thermally neutral reduction and endothermic reduction stage.
The combined steam and dry reforming of glycerol generated that syngas ratio of 2.3–3.6, where carbon balances closed within ±7 % with no carbon deposition, whilst maintaining CH4 formation below 1 vol% and a carbon conversion of >95 %. The results confirm that CLR of glycerol can deliver stable redox cycles, favourable syngas composition for downstream Fischer-Tropsch or methanol synthesis and enhances process efficiency for biofuel production and CO2 mitigation., The authors would like to acknowledge EU Horizon 2020 research and innovation programme under grant agreement no. 884197 (GLAMOUR project)., Peer reviewed
Proyecto: EC/H2020/884197