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PUBLICATIONS
2021
Raso, Raquel; García, Lucía; Ruiz, Joaquín; Oliva, Miriam; Arauzo, Jesús
Aqueous phase hydrogenolysis of glycerol over Ni/Al-Fe catalysts without external hydrogen addition Journal Article
In: Applied Catalysis B: Environmental, vol. 283, pp. 119598, 2021, ISSN: 09263373.
@article{Raso2021,
title = {Aqueous phase hydrogenolysis of glycerol over Ni/Al-Fe catalysts without external hydrogen addition},
author = {Raquel Raso and Lucía García and Joaquín Ruiz and Miriam Oliva and Jesús Arauzo},
doi = {10.1016/j.apcatb.2020.119598},
issn = {09263373},
year = {2021},
date = {2021-04-01},
journal = {Applied Catalysis B: Environmental},
volume = {283},
pages = {119598},
publisher = {Elsevier B.V.},
abstract = {The present work studied the aqueous phase hydrogenolysis (APH) of glycerol (a by-product of biodiesel manufacturing) without external hydrogen addition to produce value-added products. A series of catalysts based on 28 molar % of Ni were prepared through co-precipitation by changing the Al/Fe molar ratio. The calcined and used catalysts were characterized by several techniques (ICP-OES, N2-physisorption, XRD, H2-TPR, NH3-TPD, FESEM and STEM). This work examines the effects of the molar ratio of Al/Fe on the physicochemical characteristics of Ni/Al-Fe catalysts and during the APH of glycerol. All the catalysts showed low carbon yields to gases and high carbon yields to liquid products, mainly 1,2-propanediol, acetol and ethylene glycol. Ni/Al3Fe1 catalyst gave the best performance in the APH of glycerol: the highest glycerol conversion (42.31 %), carbon yield to gases (6.57 %) and carbon yield to liquids (30.45%). 1,2-propanediol was the liquid product with the highest carbon selectivity (70.89%).},
keywords = {},
pubstate = {published},
tppubtype = {article}
}
Lozano, Pablo; Simón, Ana I; García, Lucía; Ruiz, Joaquín; Oliva, Miriam; Arauzo, Jesús
Influence of the Ni-Co/Al-Mg catalyst loading in the continuous aqueous phase reforming of the bio-oil aqueous fraction Journal Article
In: Processes, vol. 9, no. 1, pp. 1–17, 2021, ISSN: 22279717.
@article{Lozano2021,
title = {Influence of the Ni-Co/Al-Mg catalyst loading in the continuous aqueous phase reforming of the bio-oil aqueous fraction},
author = {Pablo Lozano and Ana I Simón and Lucía García and Joaquín Ruiz and Miriam Oliva and Jesús Arauzo},
url = {https://doi.org/10.3390/pr9010081},
doi = {10.3390/pr9010081},
issn = {22279717},
year = {2021},
date = {2021-01-01},
journal = {Processes},
volume = {9},
number = {1},
pages = {1--17},
publisher = {MDPI AG},
abstract = {The effect of catalyst loading in the Aqueous Phase Reforming (APR) of bio-oil aqueous fraction has been studied with a Ni-Co/Al-Mg coprecipitated catalyst. Because of the high content of water in the bio-oil aqueous fraction, APR could be a useful process to convert this fraction into valuable products. Experiments of APR with continuous feeding of aqueous solution of acetol, butanol and acetic acid as the only compound, together with a simulated and a real aqueous fraction of bio-oil, were carried out. Liquid products in the liquid effluent of the APR model compounds were quantified and the reaction pathways were revised. The increase of catalyst loading produced an increase of gas production and a gas with higher alkanes content. Acetol was the compound with the highest reactivity while the conversion of acetic acid was very low. The presence of acetic acid in the feed caused catalyst deactivation.},
keywords = {},
pubstate = {published},
tppubtype = {article}
}
2020
Raso, Raquel; García, Lucia; Ruiz, Joaquín; Oliva, Miriam; Arauzo, Jesús
Study of Ni/Al-Fe Catalyst Stability in the Aqueous Phase Hydrogenolysis of Glycerol Journal Article
In: Catalysts 2020, Vol. 10, Page 1482, vol. 10, no. 12, pp. 1482, 2020, ISSN: 2073-4344.
@article{Raso2020,
title = {Study of Ni/Al-Fe Catalyst Stability in the Aqueous Phase Hydrogenolysis of Glycerol},
author = {Raquel Raso and Lucia García and Joaquín Ruiz and Miriam Oliva and Jesús Arauzo},
url = {https://www.mdpi.com/2073-4344/10/12/1482/htm https://www.mdpi.com/2073-4344/10/12/1482},
doi = {10.3390/CATAL10121482},
issn = {2073-4344},
year = {2020},
date = {2020-12-01},
journal = {Catalysts 2020, Vol. 10, Page 1482},
volume = {10},
number = {12},
pages = {1482},
publisher = {Multidisciplinary Digital Publishing Institute},
abstract = {The present work studied the stability and reusability of Ni/Al-Fe catalyst in the aqueous phase hydrogenolysis of glycerol without external hydrogen addition. The catalyst based on 28 molar % of Ni with 3/1 molar ratio of Al/Fe was prepared through co-precipitation. This catalyst presented the best performance in our last study which compares several Ni/Al-Fe catalysts with different molar ratios of Al/Fe. To see the influence of the pressurized water on the physicochemical characteristics of Ni/Al-Fe catalyst, a test of up to 9 h has been carried out. Fresh and used catalysts were characterized by various techniques: X-ray Diffraction (XRD), N2-physisorption, field emission scanning electron microscopy (FESEM) and STEM. Glycerol conversion and carbon yield to gases and liquids did not vary significantly when compared at 3 h and 9 h. Furthermore, the morphology of the catalyst remains stable after continuous recycling under severe hydrothermal conditions. The nickel rich phase of the catalyst, which was determined by XRD and scanning transmission electron microscopy (STEM) techniques, showed a stable size after 9 h under reaction.},
keywords = {},
pubstate = {published},
tppubtype = {article}
}
2018
García, Lucía; Valiente, Ana; Oliva, Miriam; Ruiz, Joaquín; Arauzo, Jesús
Influence of operating variables on the aqueous-phase reforming of glycerol over a Ni/Al coprecipitated catalyst Journal Article
In: International Journal of Hydrogen Energy, vol. 43, no. 45, pp. 20392–20407, 2018, ISSN: 03603199.
@article{Garcia2018,
title = {Influence of operating variables on the aqueous-phase reforming of glycerol over a Ni/Al coprecipitated catalyst},
author = {Lucía García and Ana Valiente and Miriam Oliva and Joaquín Ruiz and Jesús Arauzo},
doi = {10.1016/j.ijhydene.2018.09.119},
issn = {03603199},
year = {2018},
date = {2018-11-01},
journal = {International Journal of Hydrogen Energy},
volume = {43},
number = {45},
pages = {20392--20407},
publisher = {Elsevier Ltd},
abstract = {A systematic study focused on the aqueous-phase reforming of glycerol has been carried out in order to analyze the influence of several operating variables (system pressure, reaction temperature, glycerol content in feed, liquid feeding rate and catalyst weight/glycerol flow rate ratio) on the gas and liquid products. A continuous flow bench scale installation and a Ni/Al coprecipitated catalyst were employed. The system pressure was varied from 28 to 40 absolute bar, the reaction temperature was analyzed from 495 to 510 K, the glycerol content in the feed was studied from 2 to 10 wt%, the liquid feeding rate was changed from 0.5 to 3.0 mL/min and the catalyst weight/glycerol flow rate ratio varied from 10 to 40 g catalyst min/g glycerol. The main gas products obtained were H2, CO2 and CH4, while the main liquid products were 1,2-propanediol, ethylene glycol, acetol and ethanol. A W/mglycerol ratio of 40 g catalyst min/g glycerol, 34 bar, 500 K, 5 wt% glycerol and 1 mL/min, resulted in a high yield to H2 (6.8%), the highest yield to alkanes (10.7%), the highest 1,2-propanediol yield (0.20 g/g glycerol) and the highest ethylene glycol yield (0.11 g/g glycerol). The highest acetol yield (0.06 g/g glycerol) was obtained at 34 bar, 500 K, 5 wt% glycerol, 20 g catalyst min/g glycerol and 3 mL/min.},
keywords = {},
pubstate = {published},
tppubtype = {article}
}
Remón, Javier; Arcelus-Arrillaga, P; García, Lucía; Arauzo, Jesús
Simultaneous production of gaseous and liquid biofuels from the synergetic co-valorisation of bio-oil and crude glycerol in supercritical water Journal Article
In: Applied Energy, vol. 228, pp. 2275–2287, 2018, ISSN: 03062619.
@article{Remon2018,
title = {Simultaneous production of gaseous and liquid biofuels from the synergetic co-valorisation of bio-oil and crude glycerol in supercritical water},
author = {Javier Remón and P Arcelus-Arrillaga and Lucía García and Jesús Arauzo},
doi = {10.1016/j.apenergy.2018.07.093},
issn = {03062619},
year = {2018},
date = {2018-10-01},
journal = {Applied Energy},
volume = {228},
pages = {2275--2287},
publisher = {Elsevier Ltd},
abstract = {This work addresses the co-valorisation in supercritical water of bio-oil obtained from the fast pyrolysis of wood and crude glycerol yielded as a by-product during biodiesel production. The experiments were conducted at 380 °C and 230 bar for 30 min with a Ni-Co/Al-Mg catalyst, analysing the effects on the process of the catalyst loading (0–0.25 g catalyst/g organics) and feed composition (each material alone and all possible binary mixtures). The yields to gas, upgraded bio-oil (liquid) and solid varied as follows: 4–87%, 0–46% and 0–18%, respectively. A synergistic interaction between crude glycerol and bio-oil took place during the upgrading process, which allowed the complete and simultaneous transformation of both materials into gas and liquid bio-fuels with a negligible solid formation. The compositions of the gas and the upgraded liquid can be easy tailored by adjusting the catalyst amount and the composition of the feed. The gas phase was made up of H2 (7–49 vol.%), CO2 (31–56 vol.), CO (0–7 vol.%) and CH4 (6–57 vol.%) and had a Lower Heating Value (LHV) ranging from 8 to 22 MJ/m3 STP. The upgraded bio-oil consisted of a mixture of carboxylic acids (0–73%), furans (0–7%), phenols (0–85%), ketones (0–22%) and cyclic compounds (0–53%). The proportions of C, H and O in the liquid shifted between 66–77 wt.%, 7–11 wt.% and 15–25 wt.%, respectively, while its Higher Heating Value (HHV) ranged from 29 to 34 MJ/kg. An optimum for the simultaneous production of gas and liquid bio-fuels was achieved with a solution having equal amounts of each material and employing a catalyst amount of 0.25 g catalyst/g organics. Under such conditions, 37% of the bio-oil was transformed into an upgraded liquid having a HHV (32 MJ/kg) two times higher than the original material (16 MJ/kg) with a negligible solid formation; the rest of the bio-oil and all the crude glycerol being converted into a rich CH4 (55 vol.%) biogas with a high LHV (21 MJ/m3 STP). This represents a step-change in future energy production and can help to establish the basis for a more efficient and sustainable biomass valorisation.},
keywords = {},
pubstate = {published},
tppubtype = {article}
}