2023
Artículos de revista
Villasana, Yanet; Armenise, Sabino; Ábrego, Javier; Atienza-Martínez, María; Hablich, Karina; Bimbela, Fernando; Cornejo, Alfonso; Gandía, Luis M.
Exploring a Low-Cost Valorization Route for Amazonian Cocoa Pod Husks through Thermochemical and Catalytic Upgrading of Pyrolysis Vapors Artículo de revista
En: ACS Omega, vol. 8, no 40, pp. 37610–37621, 2023, (Publisher: American Chemical Society).
@article{villasana_exploring_2023,
title = {Exploring a Low-Cost Valorization Route for Amazonian Cocoa Pod Husks through Thermochemical and Catalytic Upgrading of Pyrolysis Vapors},
author = {Yanet Villasana and Sabino Armenise and Javier Ábrego and María Atienza-Martínez and Karina Hablich and Fernando Bimbela and Alfonso Cornejo and Luis M. Gandía},
url = {https://doi.org/10.1021/acsomega.3c06672},
doi = {10.1021/acsomega.3c06672},
year = {2023},
date = {2023-10-01},
urldate = {2023-10-01},
journal = {ACS Omega},
volume = {8},
number = {40},
pages = {37610–37621},
abstract = {Ecuador as an international leader in the production of cocoa beans produced more than 300 000 tons in 2021; hence, the management and valorization of the 2 MM tons of waste generated annually by this industry have a strategic and socioeconomic value. Consequently, appropriate technologies to avoid environmental problems and promote sustainable development and the bioeconomy, especially considering that this is a megadiverse country, are of the utmost relevance. For this reason, we explored a low-cost pyrolysis route for valorizing cocoa pod husks from Ecuador’s Amazonian region, aiming at producing pyrolysis liquids (bio-oil), biochar, and gas as an alternative chemical source from cocoa residues in the absence of hydrogen. Downstream catalytic processing of hot pyrolysis vapors using Mo- and/or Ni-based catalysts and standalone γ-Al2O3 was applied for obtaining upgraded bio-oils in a laboratory-scale fixed bed reactor, at 500 °C in a N2 atmosphere. As a result, bimetallic catalysts increased the bio-oil aqueous phase yield by 6.6%, at the expense of the organic phase due to cracking reactions according to nuclear magnetic resonance (NMR) and gas chromatography–mass spectrometry (GC–MS) results. Overall product yield remained constant, in comparison to pyrolysis without any downstream catalytic treatment (bio-oil ∼39.0–40.0 wt % and permanent gases 24.6–26.6 wt %). Ex situ reduced and passivated MoNi/γ-Al2O3 led to the lowest organic phase and highest aqueous phase yields. The product distribution between the two liquid phases was also modified by the catalytic upgrading experiments carried out, according to heteronuclear single-quantum correlation (HSQC), total correlation spectroscopy (TOCSY), and NMR analyses. The detailed composition distribution reported here shows the chemical production potential of this residue and serves as a starting point for subsequent valorizing technologies and/or processes in the food and nonfood industry beneficiating society, environment, economy, and research.},
note = {Publisher: American Chemical Society},
keywords = {},
pubstate = {published},
tppubtype = {article}
}
Ecuador as an international leader in the production of cocoa beans produced more than 300 000 tons in 2021; hence, the management and valorization of the 2 MM tons of waste generated annually by this industry have a strategic and socioeconomic value. Consequently, appropriate technologies to avoid environmental problems and promote sustainable development and the bioeconomy, especially considering that this is a megadiverse country, are of the utmost relevance. For this reason, we explored a low-cost pyrolysis route for valorizing cocoa pod husks from Ecuador’s Amazonian region, aiming at producing pyrolysis liquids (bio-oil), biochar, and gas as an alternative chemical source from cocoa residues in the absence of hydrogen. Downstream catalytic processing of hot pyrolysis vapors using Mo- and/or Ni-based catalysts and standalone γ-Al2O3 was applied for obtaining upgraded bio-oils in a laboratory-scale fixed bed reactor, at 500 °C in a N2 atmosphere. As a result, bimetallic catalysts increased the bio-oil aqueous phase yield by 6.6%, at the expense of the organic phase due to cracking reactions according to nuclear magnetic resonance (NMR) and gas chromatography–mass spectrometry (GC–MS) results. Overall product yield remained constant, in comparison to pyrolysis without any downstream catalytic treatment (bio-oil ∼39.0–40.0 wt % and permanent gases 24.6–26.6 wt %). Ex situ reduced and passivated MoNi/γ-Al2O3 led to the lowest organic phase and highest aqueous phase yields. The product distribution between the two liquid phases was also modified by the catalytic upgrading experiments carried out, according to heteronuclear single-quantum correlation (HSQC), total correlation spectroscopy (TOCSY), and NMR analyses. The detailed composition distribution reported here shows the chemical production potential of this residue and serves as a starting point for subsequent valorizing technologies and/or processes in the food and nonfood industry beneficiating society, environment, economy, and research.
Alvira, Darío; Antorán, Daniel; Vidal, Mariano; Sebastián, Víctor; Manyà, Joan Josep
Vine Shoots-Derived Hard Carbons as Anodes for Sodium-Ion Batteries: Role of Annealing Temperature in Regulating Their Structure and Morphology Artículo de revista
En: Batteries & Supercaps, vol. n/a, no n/a, pp. e202300233, 2023, ISSN: 2566-6223, (_eprint: https://onlinelibrary.wiley.com/doi/pdf/10.1002/batt.202300233).
@article{alvira_vine_nodate,
title = {Vine Shoots-Derived Hard Carbons as Anodes for Sodium-Ion Batteries: Role of Annealing Temperature in Regulating Their Structure and Morphology},
author = {Darío Alvira and Daniel Antorán and Mariano Vidal and Víctor Sebastián and Joan Josep Manyà},
url = {https://onlinelibrary.wiley.com/doi/abs/10.1002/batt.202300233},
doi = {10.1002/batt.202300233},
issn = {2566-6223},
year = {2023},
date = {2023-08-02},
urldate = {2023-08-02},
journal = {Batteries & Supercaps},
volume = {n/a},
number = {n/a},
pages = {e202300233},
abstract = {Sodium-ion batteries (SIBs) are considered one of the most promising large-scale and low-cost energy storage systems due to the abundance and low price of sodium. Herein, hard carbons from a sustainable biomass feedstock (vine shoots) were synthesized via a simple two-step carbonization process at different highest temperatures to be used as anodes in SIBs. The hard carbon produced at 1200 °C delivered the highest reversible capacity (270 mAh g−1 at 0.03 A g−1, with an acceptable initial coulombic efficiency of 71 %) since a suitable balance between the pseudographitic domains growth and the retention of microporosity, defects, and functional groups was achieved. A prominent cycling stability with a capacity retention of 97 % over 315 cycles was also attained. Comprehensive characterization unraveled a three-stage sodium storage mechanism based on adsorption, intercalation, and filling of pores. A remarkable specific capacity underestimation of up to 38 % was also found when a two-electrode half-cell configuration was employed to measure the rate performance. To avoid this systematic error caused by the counter/reference electrode polarization, we strongly recommend the use of a three-electrode setup or a full-cell configuration to correctly evaluate the anode response at moderate and high current rates.},
note = {_eprint: https://onlinelibrary.wiley.com/doi/pdf/10.1002/batt.202300233},
keywords = {},
pubstate = {published},
tppubtype = {article}
}
Sodium-ion batteries (SIBs) are considered one of the most promising large-scale and low-cost energy storage systems due to the abundance and low price of sodium. Herein, hard carbons from a sustainable biomass feedstock (vine shoots) were synthesized via a simple two-step carbonization process at different highest temperatures to be used as anodes in SIBs. The hard carbon produced at 1200 °C delivered the highest reversible capacity (270 mAh g−1 at 0.03 A g−1, with an acceptable initial coulombic efficiency of 71 %) since a suitable balance between the pseudographitic domains growth and the retention of microporosity, defects, and functional groups was achieved. A prominent cycling stability with a capacity retention of 97 % over 315 cycles was also attained. Comprehensive characterization unraveled a three-stage sodium storage mechanism based on adsorption, intercalation, and filling of pores. A remarkable specific capacity underestimation of up to 38 % was also found when a two-electrode half-cell configuration was employed to measure the rate performance. To avoid this systematic error caused by the counter/reference electrode polarization, we strongly recommend the use of a three-electrode setup or a full-cell configuration to correctly evaluate the anode response at moderate and high current rates.
Afailal, Zainab; Gil-Lalaguna, Noemí; Macías, Robert J.; Gonzalo, Alberto; Sánchez, José Luis
Production of Antioxidant Additives and High-quality Activated Biochar from Pyrolysis of Argan Shells Artículo de revista
En: BioEnergy Research, 2023, ISSN: 1939-1242.
@article{afailal_production_2023,
title = {Production of Antioxidant Additives and High-quality Activated Biochar from Pyrolysis of Argan Shells},
author = {Zainab Afailal and Noemí Gil-Lalaguna and Robert J. Macías and Alberto Gonzalo and José Luis Sánchez},
url = {https://doi.org/10.1007/s12155-023-10652-0},
doi = {10.1007/s12155-023-10652-0},
issn = {1939-1242},
year = {2023},
date = {2023-08-01},
urldate = {2023-08-01},
journal = {BioEnergy Research},
abstract = {An integral valorization route based on a pyrolysis process has been proposed to find sustainable applications for argan shells focused on the simultaneous production of activated biochar and antioxidant additives from bio-oil. The bio-oil obtained in the pyrolysis process was furtherly upgraded (hydrothermal treatment and extraction process) to obtain antioxidant additives. On the other hand, the biochar obtained in the pyrolysis was used as a feedstock to produce high-quality activated biochar (by physical activation with CO2). The increase in the pyrolysis temperature (350–550 °C) hardly affected the pyrolysis products distribution (biochar yields of 28–34 wt.% and bio-oil yields between 51 and 55 wt.%), but it led to a slight decrease in the content of phenolic monomers extracted from bio-oil (from 63 wt.% at 350 °C to 53 wt.% at 550 °C). When these extracted fractions were blended with biodiesel (<1 wt.%), improvements of up to 300% in biodiesel oxidation stability were attained. The hydrothermal treatment of the bio-oil did not show noteworthy effects either on the production or antioxidant performance of the extracted fractions if compared with the fractions extracted from the raw bio-oil. Regarding the valorization of argan shells biochar, the activated biochar prepared from it showed considerable potential as an adsorbent material for CO2 (125 mg of CO2 per g of the activated biochar) or phenols (complete removal of 99.6% in 4 h of contact time). It was characterized by a high BET surface area (up to 1500 m2/g), a high carbon content (up to 95 wt.%), low ash content (around 2 wt.%), and a pH of around 8.},
keywords = {},
pubstate = {published},
tppubtype = {article}
}
An integral valorization route based on a pyrolysis process has been proposed to find sustainable applications for argan shells focused on the simultaneous production of activated biochar and antioxidant additives from bio-oil. The bio-oil obtained in the pyrolysis process was furtherly upgraded (hydrothermal treatment and extraction process) to obtain antioxidant additives. On the other hand, the biochar obtained in the pyrolysis was used as a feedstock to produce high-quality activated biochar (by physical activation with CO2). The increase in the pyrolysis temperature (350–550 °C) hardly affected the pyrolysis products distribution (biochar yields of 28–34 wt.% and bio-oil yields between 51 and 55 wt.%), but it led to a slight decrease in the content of phenolic monomers extracted from bio-oil (from 63 wt.% at 350 °C to 53 wt.% at 550 °C). When these extracted fractions were blended with biodiesel (<1 wt.%), improvements of up to 300% in biodiesel oxidation stability were attained. The hydrothermal treatment of the bio-oil did not show noteworthy effects either on the production or antioxidant performance of the extracted fractions if compared with the fractions extracted from the raw bio-oil. Regarding the valorization of argan shells biochar, the activated biochar prepared from it showed considerable potential as an adsorbent material for CO2 (125 mg of CO2 per g of the activated biochar) or phenols (complete removal of 99.6% in 4 h of contact time). It was characterized by a high BET surface area (up to 1500 m2/g), a high carbon content (up to 95 wt.%), low ash content (around 2 wt.%), and a pH of around 8.
Antorán, Daniel; Alvira, Darío; Peker, M. Eser; Malón, Hugo; Irusta, Silvia; Sebastián, Víctor; Manyà, Joan Josep
Waste Hemp Hurd as a Sustainable Precursor for Affordable and High-Rate Hard Carbon-Based Anodes in Sodium-Ion Batteries Artículo de revista
En: Energy Fuels, vol. 37, no 13, pp. 9650–9661, 2023, ISSN: 0887-0624, (Publisher: American Chemical Society).
@article{antoran_waste_2023,
title = {Waste Hemp Hurd as a Sustainable Precursor for Affordable and High-Rate Hard Carbon-Based Anodes in Sodium-Ion Batteries},
author = {Daniel Antorán and Darío Alvira and M. Eser Peker and Hugo Malón and Silvia Irusta and Víctor Sebastián and Joan Josep Manyà},
url = {https://doi.org/10.1021/acs.energyfuels.3c01040},
doi = {10.1021/acs.energyfuels.3c01040},
issn = {0887-0624},
year = {2023},
date = {2023-07-01},
urldate = {2023-07-01},
journal = {Energy Fuels},
volume = {37},
number = {13},
pages = {9650–9661},
abstract = {The present study reports the promising potential of waste hemp-hurd-derived carbons as anodes in sodium-ion batteries (SIBs). Carbons were produced through an easily scalable process consisting of pyrolysis of raw biomass at 500 °C followed by mild chemical activation of the resulting char through wet impregnation with K2CO3 and subsequent heating of the solid phase (after filtration and drying) up to 700 or 800 °C under nitrogen. The best electrochemical performance was observed for the hard carbon activated at a char-K2CO3 mass ratio of 1:4 and heated up to 800 °C, which exhibited an excellent initial coulombic efficiency (73%) and achieved reversible charge capacities of 267 and 79 mAh g–1 at 0.03 and 1 A g–1, respectively. This material also exhibited an impressive cyclic stability and rate capability, with a capacity retention of 96% after 300 cycles at a current density of 2 A g–1. This more than satisfactory performance could be related to the textural and structural features of the hard carbon, which include moderate interconnected microporosity (with pore sizes below 1 nm), an appropriate concentration of defects in the carbon structure, relatively large interplanar distances, and a certain number of closed pores.},
note = {Publisher: American Chemical Society},
keywords = {},
pubstate = {published},
tppubtype = {article}
}
The present study reports the promising potential of waste hemp-hurd-derived carbons as anodes in sodium-ion batteries (SIBs). Carbons were produced through an easily scalable process consisting of pyrolysis of raw biomass at 500 °C followed by mild chemical activation of the resulting char through wet impregnation with K2CO3 and subsequent heating of the solid phase (after filtration and drying) up to 700 or 800 °C under nitrogen. The best electrochemical performance was observed for the hard carbon activated at a char-K2CO3 mass ratio of 1:4 and heated up to 800 °C, which exhibited an excellent initial coulombic efficiency (73%) and achieved reversible charge capacities of 267 and 79 mAh g–1 at 0.03 and 1 A g–1, respectively. This material also exhibited an impressive cyclic stability and rate capability, with a capacity retention of 96% after 300 cycles at a current density of 2 A g–1. This more than satisfactory performance could be related to the textural and structural features of the hard carbon, which include moderate interconnected microporosity (with pore sizes below 1 nm), an appropriate concentration of defects in the carbon structure, relatively large interplanar distances, and a certain number of closed pores.
Raso, Raquel; Lete, Alejandro; García, Lucía; Ruiz, Joaquín; Oliva, Miriam; Arauzo, Jesús
Aqueous phase hydrogenolysis of glycerol with in situ generated hydrogen over Ni/Al3Fe1 catalyst: effect of the calcination temperature Artículo de revista
En: RSC Advances, vol. 13, no 8, pp. 5483–5495, 2023, ISSN: 2046-2069, (Publisher: The Royal Society of Chemistry).
@article{raso_aqueous_2023,
title = {Aqueous phase hydrogenolysis of glycerol with in situ generated hydrogen over Ni/Al3Fe1 catalyst: effect of the calcination temperature},
author = {Raquel Raso and Alejandro Lete and Lucía García and Joaquín Ruiz and Miriam Oliva and Jesús Arauzo},
url = {https://pubs.rsc.org/en/content/articlelanding/2023/ra/d2ra07929a},
doi = {10.1039/D2RA07929A},
issn = {2046-2069},
year = {2023},
date = {2023-02-01},
urldate = {2023-02-01},
journal = {RSC Advances},
volume = {13},
number = {8},
pages = {5483–5495},
abstract = {The present work studied the influence of the calcination temperature on the aqueous phase hydrogenolysis of glycerol with in situ generated hydrogen over a Ni/Al3Fe1 catalyst. The Ni/Al3Fe1 catalyst was synthesized by the co-precipitation method at 28 mol% of Ni (Ni/(Ni + Al + Fe)) and a molar ratio of Al/Fe of 3/1. The prepared catalyst was calcined at different temperatures (500–750 °C). The obtained samples were tested for the aqueous phase hydrogenolysis (APH) of glycerol and characterized by several analytical techniques (ICP-OES, H2-TPR, XRD, N2-physisorption, NH3-TPD, STEM, FESEM, and TGA). The catalyst calcined at 625 °C was selected as the best sample due to its high acidity, metal dispersion, and catalytic activity; 1,2-propanediol was the highest carbon selectivity product. In addition, it experienced lower metal leaching than the catalyst calcined at 500 °C.},
note = {Publisher: The Royal Society of Chemistry},
keywords = {},
pubstate = {published},
tppubtype = {article}
}
The present work studied the influence of the calcination temperature on the aqueous phase hydrogenolysis of glycerol with in situ generated hydrogen over a Ni/Al3Fe1 catalyst. The Ni/Al3Fe1 catalyst was synthesized by the co-precipitation method at 28 mol% of Ni (Ni/(Ni + Al + Fe)) and a molar ratio of Al/Fe of 3/1. The prepared catalyst was calcined at different temperatures (500–750 °C). The obtained samples were tested for the aqueous phase hydrogenolysis (APH) of glycerol and characterized by several analytical techniques (ICP-OES, H2-TPR, XRD, N2-physisorption, NH3-TPD, STEM, FESEM, and TGA). The catalyst calcined at 625 °C was selected as the best sample due to its high acidity, metal dispersion, and catalytic activity; 1,2-propanediol was the highest carbon selectivity product. In addition, it experienced lower metal leaching than the catalyst calcined at 500 °C.
Afailal, Zainab; Gil-Lalaguna, Noemí; Fonts, Isabel; Gonzalo, Alberto; Arauzo, Jesús; Sánchez, José Luis
Thermochemical valorization of argan nutshells: Torrefaction and air–steam gasification Artículo de revista
En: Fuel, vol. 332, pp. 125970, 2023, ISSN: 0016-2361.
@article{Afailal2023,
title = {Thermochemical valorization of argan nutshells: Torrefaction and air–steam gasification},
author = {Zainab Afailal and Noemí Gil-Lalaguna and Isabel Fonts and Alberto Gonzalo and Jesús Arauzo and José Luis Sánchez},
url = {https://linkinghub.elsevier.com/retrieve/pii/S0016236122027946},
doi = {10.1016/J.FUEL.2022.125970},
issn = {0016-2361},
year = {2023},
date = {2023-01-01},
urldate = {2023-01-01},
journal = {Fuel},
volume = {332},
pages = {125970},
publisher = {Elsevier},
keywords = {},
pubstate = {published},
tppubtype = {article}
}
Balmuk, Gizem; Videgain, María; Manyà, Joan Josep; Duman, Gozde; Yanik, Jale
Effects of pyrolysis temperature and pressure on agronomic properties of biochar Artículo de revista
En: Journal of Analytical and Applied Pyrolysis, vol. 169, no May, pp. 105858, 2023, ISSN: 01652370.
@article{Balmuk2023,
title = {Effects of pyrolysis temperature and pressure on agronomic properties of biochar},
author = {Gizem Balmuk and María Videgain and Joan Josep Manyà and Gozde Duman and Jale Yanik},
url = {https://doi.org/10.1016/j.jaap.2022.105728 https://linkinghub.elsevier.com/retrieve/pii/S0165237023000025},
doi = {10.1016/j.jaap.2023.105858},
issn = {01652370},
year = {2023},
date = {2023-01-01},
urldate = {2023-01-01},
journal = {Journal of Analytical and Applied Pyrolysis},
volume = {169},
number = {May},
pages = {105858},
keywords = {},
pubstate = {published},
tppubtype = {article}
}
2022
Artículos de revista
Alvira, Darío; Antorán, Daniel; Manyà, Joan Josep
Assembly and electrochemical testing of renewable carbon-based anodes in SIBs: A practical guide Artículo de revista
En: Journal of Energy Chemistry, vol. 75, pp. 457–477, 2022, ISSN: 2095-4956.
@article{Alvira2022b,
title = {Assembly and electrochemical testing of renewable carbon-based anodes in SIBs: A practical guide},
author = {Darío Alvira and Daniel Antorán and Joan Josep Manyà},
url = {https://linkinghub.elsevier.com/retrieve/pii/S209549562200479X},
doi = {10.1016/J.JECHEM.2022.09.002},
issn = {2095-4956},
year = {2022},
date = {2022-12-01},
urldate = {2022-12-01},
journal = {Journal of Energy Chemistry},
volume = {75},
pages = {457--477},
publisher = {Elsevier},
keywords = {},
pubstate = {published},
tppubtype = {article}
}
Alvira, Darío; Antorán, Daniel; Manyà, Joan Josep
Plant-derived hard carbon as anode for sodium-ion batteries: A comprehensive review to guide interdisciplinary research Artículo de revista
En: Chemical Engineering Journal, vol. 447, pp. 137468, 2022, ISSN: 1385-8947.
@article{Alvira2022,
title = {Plant-derived hard carbon as anode for sodium-ion batteries: A comprehensive review to guide interdisciplinary research},
author = {Darío Alvira and Daniel Antorán and Joan Josep Manyà},
url = {https://linkinghub.elsevier.com/retrieve/pii/S1385894722029564},
doi = {10.1016/J.CEJ.2022.137468},
issn = {1385-8947},
year = {2022},
date = {2022-11-01},
urldate = {2022-11-01},
journal = {Chemical Engineering Journal},
volume = {447},
pages = {137468},
publisher = {Elsevier},
keywords = {},
pubstate = {published},
tppubtype = {article}
}
Marrodán, Lorena; Millera, Ángela; Bilbao, Rafael; Alzueta, María U
An experimental and modeling study of acetylene-dimethyl ether mixtures oxidation at high-pressure Artículo de revista
En: Fuel, vol. 327, pp. 125143, 2022, ISSN: 0016-2361.
@article{Marrodan2022,
title = {An experimental and modeling study of acetylene-dimethyl ether mixtures oxidation at high-pressure},
author = {Lorena Marrodán and Ángela Millera and Rafael Bilbao and María U Alzueta},
url = {https://linkinghub.elsevier.com/retrieve/pii/S0016236122019846},
doi = {10.1016/J.FUEL.2022.125143},
issn = {0016-2361},
year = {2022},
date = {2022-11-01},
urldate = {2022-11-01},
journal = {Fuel},
volume = {327},
pages = {125143},
publisher = {Elsevier},
keywords = {},
pubstate = {published},
tppubtype = {article}
}
Gil-Lalaguna, Noemí; Navarro-Gil, África; Carstensen, Hans-Heinrich; Ruiz, Joaquín; Fonts, Isabel; Ceamanos, Jesús; Murillo, María Benita; Gea, Gloria
CO2 adsorption on pyrolysis char from protein-containing livestock waste: How do proteins affect? Artículo de revista
En: Science of The Total Environment, vol. 846, pp. 157395, 2022, ISSN: 0048-9697.
@article{Gil-Lalaguna2022,
title = {CO2 adsorption on pyrolysis char from protein-containing livestock waste: How do proteins affect?},
author = {Noemí Gil-Lalaguna and África Navarro-Gil and Hans-Heinrich Carstensen and Joaquín Ruiz and Isabel Fonts and Jesús Ceamanos and María Benita Murillo and Gloria Gea},
doi = {10.1016/J.SCITOTENV.2022.157395},
issn = {0048-9697},
year = {2022},
date = {2022-11-01},
urldate = {2022-11-01},
journal = {Science of The Total Environment},
volume = {846},
pages = {157395},
publisher = {Elsevier},
abstract = {Biogas generation through anaerobic digestion provides an interesting opportunity to valorize some types of animal waste materials whose management is increasingly complicated by legal and environmental restrictions. To successfully expand anaerobic digestion in livestock areas, operational issues such as digestate management must be addressed in an economical and environmentally sustainable way. Biogas upgrading is another necessary stage before intending it to add-value applications. The high concentration of CO2 in biogas results in a reduced caloric value, so the removal of CO2 would be beneficial for most end-users. The current work evaluates the CO2 uptake properties (thermogravimetry study) of low-cost adsorbent materials produced from the animal wastes generated in the livestock area itself, specifically via pyrolysis of poorly biodegradable materials, such as meat and bone meal, and the digestate from manure anaerobic digestion. Therefore, the new element in this study with respect to other studies found in the literature related to biochar-based CO2 adsorption performance is the presence of high content of pyrolyzed proteins in the adsorbent material. In this work, pyrolyzed chars from both meat and bone meal and co-digested manure have been proven to adsorb CO2 reversibly, and also the chars produced from their representative pure proteins (collagen and soybean protein), which were evaluated as model compounds for a better understanding of the individual performance of proteins. The ultra-microporosity developed in the protein chars during pyrolysis seems to be the main explanation for such CO2 uptake capacities, while neither the BET surface area nor N-functionalities on the char surface can properly explain the observed results. Although the CO2 adsorption capacities of these pristine chars (6–41.0 mg CO2/g char) are far away from data of commercially activated carbons ($sim$80 mg CO2/g char), this application opens a new via to integrate and valorize these wastes in the circular economy of the primary sector.},
keywords = {},
pubstate = {published},
tppubtype = {article}
}
Biogas generation through anaerobic digestion provides an interesting opportunity to valorize some types of animal waste materials whose management is increasingly complicated by legal and environmental restrictions. To successfully expand anaerobic digestion in livestock areas, operational issues such as digestate management must be addressed in an economical and environmentally sustainable way. Biogas upgrading is another necessary stage before intending it to add-value applications. The high concentration of CO2 in biogas results in a reduced caloric value, so the removal of CO2 would be beneficial for most end-users. The current work evaluates the CO2 uptake properties (thermogravimetry study) of low-cost adsorbent materials produced from the animal wastes generated in the livestock area itself, specifically via pyrolysis of poorly biodegradable materials, such as meat and bone meal, and the digestate from manure anaerobic digestion. Therefore, the new element in this study with respect to other studies found in the literature related to biochar-based CO2 adsorption performance is the presence of high content of pyrolyzed proteins in the adsorbent material. In this work, pyrolyzed chars from both meat and bone meal and co-digested manure have been proven to adsorb CO2 reversibly, and also the chars produced from their representative pure proteins (collagen and soybean protein), which were evaluated as model compounds for a better understanding of the individual performance of proteins. The ultra-microporosity developed in the protein chars during pyrolysis seems to be the main explanation for such CO2 uptake capacities, while neither the BET surface area nor N-functionalities on the char surface can properly explain the observed results. Although the CO2 adsorption capacities of these pristine chars (6–41.0 mg CO2/g char) are far away from data of commercially activated carbons ($sim$80 mg CO2/g char), this application opens a new via to integrate and valorize these wastes in the circular economy of the primary sector.
Marrodán, Lorena; Millera, Ángela; Bilbao, Rafael; Alzueta, María U
Experimental and Modeling Evaluation of Dimethoxymethane as an Additive for High-Pressure Acetylene Oxidation Artículo de revista
En: The Journal of Physical Chemistry A, vol. 2022, pp. 6263, 2022, ISSN: 1089-5639.
@article{Marrodan2022b,
title = {Experimental and Modeling Evaluation of Dimethoxymethane as an Additive for High-Pressure Acetylene Oxidation},
author = {Lorena Marrodán and Ángela Millera and Rafael Bilbao and María U Alzueta},
url = {https://pubs.acs.org/doi/full/10.1021/acs.jpca.2c03130},
doi = {10.1021/ACS.JPCA.2C03130},
issn = {1089-5639},
year = {2022},
date = {2022-09-01},
urldate = {2022-09-01},
journal = {The Journal of Physical Chemistry A},
volume = {2022},
pages = {6263},
publisher = {American Chemical Society},
abstract = {The high-pressure oxidation of acetylene–dimethoxymethane (C2H2–DMM) mixtures in a tubular flow reactor has been analyzed from both experimental and modeling perspectives. In addition to pressure (...},
keywords = {},
pubstate = {published},
tppubtype = {article}
}
The high-pressure oxidation of acetylene–dimethoxymethane (C2H2–DMM) mixtures in a tubular flow reactor has been analyzed from both experimental and modeling perspectives. In addition to pressure (…
Bourgalais, Jérémy; Carstensen, Hans-Heinrich; Herbinet, Olivier; Garcia, Gustavo A.; Arnoux, Philippe; Tran, Luc-Sy; Vanhove, Guillaume; Nahon, Laurent; Hochlaf, Majdi; Battin-Leclerc, Frédérique
Product Identification in the Low-Temperature Oxidation of Cyclohexane Using a Jet-Stirred Reactor in Combination with SVUV-PEPICO Analysis and Theoretical Quantum Calculations Artículo de revista
En: The Journal of Physical Chemistry A, vol. 126, no 34, pp. 5784–5799, 2022, ISSN: 1089-5639.
@article{Bourgalais2022,
title = {Product Identification in the Low-Temperature Oxidation of Cyclohexane Using a Jet-Stirred Reactor in Combination with SVUV-PEPICO Analysis and Theoretical Quantum Calculations},
author = {Jérémy Bourgalais and Hans-Heinrich Carstensen and Olivier Herbinet and Gustavo A. Garcia and Philippe Arnoux and Luc-Sy Tran and Guillaume Vanhove and Laurent Nahon and Majdi Hochlaf and Frédérique Battin-Leclerc},
url = {https://pubs.acs.org/doi/full/10.1021/acs.jpca.2c04490},
doi = {10.1021/ACS.JPCA.2C04490/ASSET/IMAGES/MEDIUM/JP2C04490_0020.GIF},
issn = {1089-5639},
year = {2022},
date = {2022-09-01},
journal = {The Journal of Physical Chemistry A},
volume = {126},
number = {34},
pages = {5784--5799},
publisher = {American Chemical Society (ACS)},
abstract = {Cyclohexane oxidation chemistry was investigated using a near-atmospheric pressure jet-stirred reactor at T = 570 K and equivalence ratio ϕ = 0.8. Numerous intermediates including hydroperoxides an...},
keywords = {},
pubstate = {published},
tppubtype = {article}
}
Cyclohexane oxidation chemistry was investigated using a near-atmospheric pressure jet-stirred reactor at T = 570 K and equivalence ratio ϕ = 0.8. Numerous intermediates including hydroperoxides an…
Tran, Luc Sy; Herbinet, Olivier; Carstensen, Hans-Heinrich; Battin-Leclerc, Frédérique
Chemical kinetics of cyclic ethers in combustion Artículo de revista
En: Progress in Energy and Combustion Science, vol. 92, pp. 101019, 2022, ISSN: 0360-1285.
@article{Tran2022,
title = {Chemical kinetics of cyclic ethers in combustion},
author = {Luc Sy Tran and Olivier Herbinet and Hans-Heinrich Carstensen and Frédérique Battin-Leclerc},
doi = {10.1016/J.PECS.2022.101019},
issn = {0360-1285},
year = {2022},
date = {2022-09-01},
urldate = {2022-09-01},
journal = {Progress in Energy and Combustion Science},
volume = {92},
pages = {101019},
publisher = {Pergamon},
abstract = {Cyclic Ethers (CEs) belong to a class of compounds of importance to understand the chemistry of both the engine auto-ignition of hydrocarbon fuels and the combustion of oxygenated biofuels. This article, divided in six parts, aims at systematically analyzing how up-to-date experimental and theoretical methods were applied to unveil the gas-phase oxidation chemistry of these compounds. The first part gives a brief overview on the significance of CEs as intermediates formed during alkane low-temperature oxidation summarizing its generally accepted chemical mechanism. This part also addresses the role of CEs as potential biofuels derived from lignocellulosic biomass and discusses the production methods of these molecules and their combustion performances in engine. The second part presents the different theoretical methods dedicated to calculate the electronic structure, thermochemical and kinetic data of CEs. The third part introduces the experimental methods used in studies related to CEs with a special focus on mass spectrometry and gas chromatography. The fourth part reviews the experimental and modeling studies related to CE formation during the low-temperature oxidation of linear, branched, cyclic alkanes, alkylbenzenes, olefins, and oxygenated fuels. The fifth part analyses the published work concerning the CE degradation chemistry and highlights the dominant involved reactions. To finish, the sixth part concludes and proposes future research directions.},
keywords = {},
pubstate = {published},
tppubtype = {article}
}
Cyclic Ethers (CEs) belong to a class of compounds of importance to understand the chemistry of both the engine auto-ignition of hydrocarbon fuels and the combustion of oxygenated biofuels. This article, divided in six parts, aims at systematically analyzing how up-to-date experimental and theoretical methods were applied to unveil the gas-phase oxidation chemistry of these compounds. The first part gives a brief overview on the significance of CEs as intermediates formed during alkane low-temperature oxidation summarizing its generally accepted chemical mechanism. This part also addresses the role of CEs as potential biofuels derived from lignocellulosic biomass and discusses the production methods of these molecules and their combustion performances in engine. The second part presents the different theoretical methods dedicated to calculate the electronic structure, thermochemical and kinetic data of CEs. The third part introduces the experimental methods used in studies related to CEs with a special focus on mass spectrometry and gas chromatography. The fourth part reviews the experimental and modeling studies related to CE formation during the low-temperature oxidation of linear, branched, cyclic alkanes, alkylbenzenes, olefins, and oxygenated fuels. The fifth part analyses the published work concerning the CE degradation chemistry and highlights the dominant involved reactions. To finish, the sixth part concludes and proposes future research directions.
Méndez, A.; Álvarez, M. L.; Fidalgo, J. M.; Stasi, Christian Di; Manyà, Joan Josep; Gascó, G.
Biomass-derived activated carbon as catalyst in the leaching of metals from a copper sulfide concentrate Artículo de revista
En: Minerals Engineering, vol. 183, pp. 107594, 2022, ISSN: 0892-6875.
@article{Mendez2022,
title = {Biomass-derived activated carbon as catalyst in the leaching of metals from a copper sulfide concentrate},
author = {A. Méndez and M. L. Álvarez and J. M. Fidalgo and Christian Di Stasi and Joan Josep Manyà and G. Gascó},
url = {https://linkinghub.elsevier.com/retrieve/pii/S0892687522002047},
doi = {10.1016/J.MINENG.2022.107594},
issn = {0892-6875},
year = {2022},
date = {2022-06-01},
urldate = {2022-06-01},
journal = {Minerals Engineering},
volume = {183},
pages = {107594},
publisher = {Pergamon},
keywords = {},
pubstate = {published},
tppubtype = {article}
}
Greco, Gianluca; Canevesi, Rafael L. S.; Stasi, Christian Di; Celzard, Alain; Fierro, Vanessa; Manyà, Joan Josep
Biomass-derived carbons physically activated in one or two steps for CH4/CO2 separation Artículo de revista
En: Renewable Energy, vol. 191, pp. 122–133, 2022, ISSN: 0960-1481.
@article{Greco2022,
title = {Biomass-derived carbons physically activated in one or two steps for CH4/CO2 separation},
author = {Gianluca Greco and Rafael L. S. Canevesi and Christian Di Stasi and Alain Celzard and Vanessa Fierro and Joan Josep Manyà},
url = {https://linkinghub.elsevier.com/retrieve/pii/S0960148122004967},
doi = {10.1016/J.RENENE.2022.04.035},
issn = {0960-1481},
year = {2022},
date = {2022-05-01},
urldate = {2022-05-01},
journal = {Renewable Energy},
volume = {191},
pages = {122--133},
publisher = {Pergamon},
keywords = {},
pubstate = {published},
tppubtype = {article}
}
Ilarri, Sergio; Trillo-Lado, Raquel; Marrodán, Lorena
Traffic and Pollution Modelling for Air Quality Awareness: An Experience in the City of Zaragoza Artículo de revista
En: SN Computer Science 2022 3:4, vol. 3, no 4, pp. 1–33, 2022, ISSN: 2661-8907.
@article{Ilarri2022,
title = {Traffic and Pollution Modelling for Air Quality Awareness: An Experience in the City of Zaragoza},
author = {Sergio Ilarri and Raquel Trillo-Lado and Lorena Marrodán},
url = {https://link.springer.com/article/10.1007/s42979-022-01105-0},
doi = {10.1007/S42979-022-01105-0},
issn = {2661-8907},
year = {2022},
date = {2022-05-01},
journal = {SN Computer Science 2022 3:4},
volume = {3},
number = {4},
pages = {1--33},
publisher = {Springer},
abstract = {Air pollution due to the presence of small particles and gases in the atmosphere is a major cause of health problems. In urban areas, where most of the population is concentrated, traffic is a major source of air pollutants (such as nitrogen oxides or $$hbox NO_x$$ and carbon monoxide or CO). Therefore, for smart cities, carrying out an adequate traffic monitoring is a key issue, since it can help citizens to make better decisions and public administrations to define appropriate policies. Thus, citizens could use these data to make appropriate mobility decisions. In the same way, a city council can exploit the collected data for traffic management and for the establishment of suitable traffic policies throughout the city, such as restricting the traffic flow in certain areas. For this purpose, a suitable modelling approach that provides the estimated/predicted values of pollutants at each location is needed. In this paper, an approach followed to model traffic flow and air pollution dispersion in the city of Zaragoza (Spain) is described. Our goal is to estimate the air quality in different areas of the city, to raise awareness and help citizens to make better decisions; for this purpose, traffic data play an important role. In more detail, the proposal presented includes a traffic modelling approach to estimate and predict the amount of traffic at each road segment and hour, by combining historical measurements of real traffic of vehicles and the use of the SUMO traffic simulator on real city roadmaps, along with the application of a trajectory generation strategy that complements the functionalities of SUMO (for example, SUMO's calibrators). Furthermore, a pollution modelling approach is also provided, to estimate the impact of traffic flows in terms of pollutants in the atmosphere: an R package called Vehicular Emissions INventories (VEIN) is used to estimate the amount of $$hbox NO_x$$ generated by the traffic flows by taking into account the vehicular fleet composition (i.e., the types of vehicles, their size and the type of fuel they use) of the studied area. Finally, considering this estimation of $$hbox NO_x$$ , a service capable of offering maps with the prediction of the dispersion of these atmospheric pollutants in the air has been established, which uses the Graz Lagrangian Model (GRAL) and takes into account the meteorological conditions and morphology of the city. The results obtained in the experimental evaluation of the proposal indicate a good accuracy in the modelling of traffic flows, whereas the comparison of the prediction of air pollutants with real measurements shows a general underestimation, due to some limitations of the input data considered. In any case, the results indicate that this first approach can be used for forecasting the air pollution within the city.},
keywords = {},
pubstate = {published},
tppubtype = {article}
}
Air pollution due to the presence of small particles and gases in the atmosphere is a major cause of health problems. In urban areas, where most of the population is concentrated, traffic is a major source of air pollutants (such as nitrogen oxides or $$hbox NO_x$$ and carbon monoxide or CO). Therefore, for smart cities, carrying out an adequate traffic monitoring is a key issue, since it can help citizens to make better decisions and public administrations to define appropriate policies. Thus, citizens could use these data to make appropriate mobility decisions. In the same way, a city council can exploit the collected data for traffic management and for the establishment of suitable traffic policies throughout the city, such as restricting the traffic flow in certain areas. For this purpose, a suitable modelling approach that provides the estimated/predicted values of pollutants at each location is needed. In this paper, an approach followed to model traffic flow and air pollution dispersion in the city of Zaragoza (Spain) is described. Our goal is to estimate the air quality in different areas of the city, to raise awareness and help citizens to make better decisions; for this purpose, traffic data play an important role. In more detail, the proposal presented includes a traffic modelling approach to estimate and predict the amount of traffic at each road segment and hour, by combining historical measurements of real traffic of vehicles and the use of the SUMO traffic simulator on real city roadmaps, along with the application of a trajectory generation strategy that complements the functionalities of SUMO (for example, SUMO’s calibrators). Furthermore, a pollution modelling approach is also provided, to estimate the impact of traffic flows in terms of pollutants in the atmosphere: an R package called Vehicular Emissions INventories (VEIN) is used to estimate the amount of $$hbox NO_x$$ generated by the traffic flows by taking into account the vehicular fleet composition (i.e., the types of vehicles, their size and the type of fuel they use) of the studied area. Finally, considering this estimation of $$hbox NO_x$$ , a service capable of offering maps with the prediction of the dispersion of these atmospheric pollutants in the air has been established, which uses the Graz Lagrangian Model (GRAL) and takes into account the meteorological conditions and morphology of the city. The results obtained in the experimental evaluation of the proposal indicate a good accuracy in the modelling of traffic flows, whereas the comparison of the prediction of air pollutants with real measurements shows a general underestimation, due to some limitations of the input data considered. In any case, the results indicate that this first approach can be used for forecasting the air pollution within the city.
Alexandrino, Katiuska; Millera, Ángela; Bilbao, Rafael; Alzueta, María U
Experimental and simulation study of the high pressure oxidation of dimethyl carbonate Artículo de revista
En: Fuel, vol. 309, pp. 122154, 2022, ISSN: 0016-2361.
@article{Alexandrino2022,
title = {Experimental and simulation study of the high pressure oxidation of dimethyl carbonate},
author = {Katiuska Alexandrino and Ángela Millera and Rafael Bilbao and María U Alzueta},
doi = {10.1016/J.FUEL.2021.122154},
issn = {0016-2361},
year = {2022},
date = {2022-02-01},
urldate = {2022-02-01},
journal = {Fuel},
volume = {309},
pages = {122154},
publisher = {Elsevier},
abstract = {An experimental and modeling study of the oxidation at high pressure of dimethyl carbonate (DMC) has been performed in a quartz tubular flow reactor. Experimental and simulated concentrations of DMC, CO, CO2 and H2 have been obtained for different temperatures (500–1073 K), pressures (20, 40, and 60 atm) and stoichiometries ($łambda$ = 0.7, 1, and 35). Both pressure and concentration of oxygen are important parameters for conversion of DMC. The simulations have been carried out using a detailed kinetic mechanism previously developed by the research group. In general, the model is able to reproduce the experimental trends of the different concentration profiles, although some discrepancies are observed between experimental and simulation results. The performance of the model was also evaluated through the simulation of literature data of the oxidation of DMC at atmospheric pressure in a flow reactor and of the DMC ignition delay times under low and high pressures. In this sense, this work contributes to the knowledge of the combustion process of DMC, by providing new experimental data on the conversion of DMC at high pressures and using a kinetic model for the interpretation of the results.},
keywords = {},
pubstate = {published},
tppubtype = {article}
}
An experimental and modeling study of the oxidation at high pressure of dimethyl carbonate (DMC) has been performed in a quartz tubular flow reactor. Experimental and simulated concentrations of DMC, CO, CO2 and H2 have been obtained for different temperatures (500–1073 K), pressures (20, 40, and 60 atm) and stoichiometries ($łambda$ = 0.7, 1, and 35). Both pressure and concentration of oxygen are important parameters for conversion of DMC. The simulations have been carried out using a detailed kinetic mechanism previously developed by the research group. In general, the model is able to reproduce the experimental trends of the different concentration profiles, although some discrepancies are observed between experimental and simulation results. The performance of the model was also evaluated through the simulation of literature data of the oxidation of DMC at atmospheric pressure in a flow reactor and of the DMC ignition delay times under low and high pressures. In this sense, this work contributes to the knowledge of the combustion process of DMC, by providing new experimental data on the conversion of DMC at high pressures and using a kinetic model for the interpretation of the results.
Alzueta, María U; Ara, L.; Mercader, Víctor D; Delogu, M.; Bilbao, Rafael
Interaction of NH3 and NO under combustion conditions. Experimental flow reactor study and kinetic modeling simulation Artículo de revista
En: Combustion and Flame, vol. 235, 2022, ISSN: 15562921.
@article{Alzueta2022,
title = {Interaction of NH3 and NO under combustion conditions. Experimental flow reactor study and kinetic modeling simulation},
author = {María U Alzueta and L. Ara and Víctor D Mercader and M. Delogu and Rafael Bilbao},
doi = {10.1016/j.combustflame.2021.111691},
issn = {15562921},
year = {2022},
date = {2022-01-01},
urldate = {2022-01-01},
journal = {Combustion and Flame},
volume = {235},
publisher = {Elsevier Inc.},
abstract = {The interaction between ammonia and NO under combustion conditions is analyzed in the present work, from both experimental and kinetic modelling points of view. An experimental systematic study of the influence of the main variables for the NH3[sbnd]NO interaction is made using a laboratory tubular flow reactor installation. Experiments are performed at atmospheric pressure and variables analyzed include: temperature in the 700–1500 K range, air stoichiometry, from pyrolysis to very oxidizing conditions, and the NH3/NO ratio, in the 0.7–3.5 range. Nitrogen and argon have been used as diluent gas. A literature reaction mechanism has been used to simulate the present experimental results and discuss the main findings. Reaction path analysis has allowed the identification of the reaction routes under the studied conditions. The simulations reflect the main experimental trends observed. Main results show that NO reduction by NH3 occurs at any conditions studied, but is more intense under oxygen excess conditions. Interactions of NH3 and NO proceeds in a molar basis with optimum conversions of NO of up to almost 100%.},
keywords = {},
pubstate = {published},
tppubtype = {article}
}
The interaction between ammonia and NO under combustion conditions is analyzed in the present work, from both experimental and kinetic modelling points of view. An experimental systematic study of the influence of the main variables for the NH3[sbnd]NO interaction is made using a laboratory tubular flow reactor installation. Experiments are performed at atmospheric pressure and variables analyzed include: temperature in the 700–1500 K range, air stoichiometry, from pyrolysis to very oxidizing conditions, and the NH3/NO ratio, in the 0.7–3.5 range. Nitrogen and argon have been used as diluent gas. A literature reaction mechanism has been used to simulate the present experimental results and discuss the main findings. Reaction path analysis has allowed the identification of the reaction routes under the studied conditions. The simulations reflect the main experimental trends observed. Main results show that NO reduction by NH3 occurs at any conditions studied, but is more intense under oxygen excess conditions. Interactions of NH3 and NO proceeds in a molar basis with optimum conversions of NO of up to almost 100%.
Alexandrino, Katiuska; Millera, Ángela; Bilbao, Rafael; Alzueta, María U
Experimental and simulation study of the high pressure oxidation of dimethyl carbonate Artículo de revista
En: Fuel, vol. 309, no October 2021, 2022, ISSN: 00162361.
@article{Alexandrino2022b,
title = {Experimental and simulation study of the high pressure oxidation of dimethyl carbonate},
author = {Katiuska Alexandrino and Ángela Millera and Rafael Bilbao and María U Alzueta},
doi = {10.1016/j.fuel.2021.122154},
issn = {00162361},
year = {2022},
date = {2022-01-01},
urldate = {2022-01-01},
journal = {Fuel},
volume = {309},
number = {October 2021},
abstract = {An experimental and modeling study of the oxidation at high pressure of dimethyl carbonate (DMC) has been performed in a quartz tubular flow reactor. Experimental and simulated concentrations of DMC, CO, CO2 and H2 have been obtained for different temperatures (500–1073 K), pressures (20, 40, and 60 atm) and stoichiometries ($łambda$ = 0.7, 1, and 35). Both pressure and concentration of oxygen are important parameters for conversion of DMC. The simulations have been carried out using a detailed kinetic mechanism previously developed by the research group. In general, the model is able to reproduce the experimental trends of the different concentration profiles, although some discrepancies are observed between experimental and simulation results. The performance of the model was also evaluated through the simulation of literature data of the oxidation of DMC at atmospheric pressure in a flow reactor and of the DMC ignition delay times under low and high pressures. In this sense, this work contributes to the knowledge of the combustion process of DMC, by providing new experimental data on the conversion of DMC at high pressures and using a kinetic model for the interpretation of the results.},
keywords = {},
pubstate = {published},
tppubtype = {article}
}
An experimental and modeling study of the oxidation at high pressure of dimethyl carbonate (DMC) has been performed in a quartz tubular flow reactor. Experimental and simulated concentrations of DMC, CO, CO2 and H2 have been obtained for different temperatures (500–1073 K), pressures (20, 40, and 60 atm) and stoichiometries ($łambda$ = 0.7, 1, and 35). Both pressure and concentration of oxygen are important parameters for conversion of DMC. The simulations have been carried out using a detailed kinetic mechanism previously developed by the research group. In general, the model is able to reproduce the experimental trends of the different concentration profiles, although some discrepancies are observed between experimental and simulation results. The performance of the model was also evaluated through the simulation of literature data of the oxidation of DMC at atmospheric pressure in a flow reactor and of the DMC ignition delay times under low and high pressures. In this sense, this work contributes to the knowledge of the combustion process of DMC, by providing new experimental data on the conversion of DMC at high pressures and using a kinetic model for the interpretation of the results.