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PUBLICATIONS
2011
Medrano, José A; Oliva, Miriam; Ruiz, Joaquín; García, Lucía; Arauzo, Jesús
Hydrogen from aqueous fraction of biomass pyrolysis liquids by catalytic steam reforming in fluidized bed Journal Article
In: Energy, vol. 36, no. 4, pp. 2215–2224, 2011, ISSN: 03605442.
@article{Medrano2011,
title = {Hydrogen from aqueous fraction of biomass pyrolysis liquids by catalytic steam reforming in fluidized bed},
author = {José A Medrano and Miriam Oliva and Joaquín Ruiz and Lucía García and Jesús Arauzo},
doi = {10.1016/j.energy.2010.03.059},
issn = {03605442},
year = {2011},
date = {2011-04-01},
journal = {Energy},
volume = {36},
number = {4},
pages = {2215--2224},
publisher = {Elsevier Ltd},
abstract = {Sustainable pathways for producing hydrogen as a synthesis intermediate or as a clean energetic vector will be needed in the future. Renewable biomass resources should be taken into account in this new scenario. Processing through a pyrolysis step, optimized to high liquid production (bio-oil), increases the energy bulk density of biomass for transportation. Steam reforming of the aqueous fraction is an alternative process that increases the hydrogen content of the syngas. However, the thermochemical conversion of organic compounds derived from biomass involves drawbacks such as coke formation on the catalysts. This work studies the performance of Ni-Al catalysts modified with Ca or Mg in the steam reforming of the aqueous fraction of pyrolysis liquids and the resulting coke deposits. The catalyst composition influenced the quantity and type of coke deposits. Calcium improved the formation of carbonaceous products leading to lower H2/CO ratios while magnesium improved the WGS (water gas shift) reaction. The strategy of reducing the space velocity resulted in a low coke removal although the addition of small quantities of oxygen decreased the coke content of the catalyst by more than 50% weight. Greater efficiency and further catalyst development are needed to improve the energetic requirements of the process. textcopyright 2010 Elsevier Ltd.},
keywords = {},
pubstate = {published},
tppubtype = {article}
}
Sustainable pathways for producing hydrogen as a synthesis intermediate or as a clean energetic vector will be needed in the future. Renewable biomass resources should be taken into account in this new scenario. Processing through a pyrolysis step, optimized to high liquid production (bio-oil), increases the energy bulk density of biomass for transportation. Steam reforming of the aqueous fraction is an alternative process that increases the hydrogen content of the syngas. However, the thermochemical conversion of organic compounds derived from biomass involves drawbacks such as coke formation on the catalysts. This work studies the performance of Ni-Al catalysts modified with Ca or Mg in the steam reforming of the aqueous fraction of pyrolysis liquids and the resulting coke deposits. The catalyst composition influenced the quantity and type of coke deposits. Calcium improved the formation of carbonaceous products leading to lower H2/CO ratios while magnesium improved the WGS (water gas shift) reaction. The strategy of reducing the space velocity resulted in a low coke removal although the addition of small quantities of oxygen decreased the coke content of the catalyst by more than 50% weight. Greater efficiency and further catalyst development are needed to improve the energetic requirements of the process. textcopyright 2010 Elsevier Ltd.
2010
Valiente, Ana; Medrano, José A; Oliva, Miriam; Ruiz, Joaquín; García, Lucía; Arauzo, Jesús
Bioenergy II: Hydrogen production by aqueous-phase reforming Journal Article
In: International Journal of Chemical Reactor Engineering, vol. 8, no. 1, 2010, ISSN: 15426580.
@article{Valiente2010,
title = {Bioenergy II: Hydrogen production by aqueous-phase reforming},
author = {Ana Valiente and José A Medrano and Miriam Oliva and Joaquín Ruiz and Lucía García and Jesús Arauzo},
url = {https://www.degruyter.com/view/journals/ijcre/8/1/article-ijcre.2010.8.1.1924.xml.xml},
doi = {10.2202/1542-6580.1924},
issn = {15426580},
year = {2010},
date = {2010-02-01},
journal = {International Journal of Chemical Reactor Engineering},
volume = {8},
number = {1},
publisher = {Walter de Gruyter GmbH},
abstract = {The present work is focused on the aqueous-phase reforming of ethylene glycol at 500 K. The influence of the system pressure (27 to 36 bar) and the catalyst weight/ethylene glycol flow rate ratio has been studied using a Pt/Al2O3 research catalyst. A comparison of the latter with a Ni/Al coprecipitated catalyst showed a significant influence on hydrogen and alkane selectivities. Copyright textcopyright 2010 The Berkeley Electronic Press.},
keywords = {},
pubstate = {published},
tppubtype = {article}
}
The present work is focused on the aqueous-phase reforming of ethylene glycol at 500 K. The influence of the system pressure (27 to 36 bar) and the catalyst weight/ethylene glycol flow rate ratio has been studied using a Pt/Al2O3 research catalyst. A comparison of the latter with a Ni/Al coprecipitated catalyst showed a significant influence on hydrogen and alkane selectivities. Copyright textcopyright 2010 The Berkeley Electronic Press.
2009
Bimbela, Fernando; Oliva, Miriam; Ruiz, Joaquín; García, Lucía; Arauzo, Jesús
Catalytic steam reforming of model compounds of biomass pyrolysis liquids in fixed bed: Acetol and n-butanol Journal Article
In: Journal of Analytical and Applied Pyrolysis, vol. 85, no. 1-2, pp. 204–213, 2009, ISSN: 01652370.
@article{Bimbela2009,
title = {Catalytic steam reforming of model compounds of biomass pyrolysis liquids in fixed bed: Acetol and n-butanol},
author = {Fernando Bimbela and Miriam Oliva and Joaquín Ruiz and Lucía García and Jesús Arauzo},
doi = {10.1016/j.jaap.2008.11.033},
issn = {01652370},
year = {2009},
date = {2009-05-01},
journal = {Journal of Analytical and Applied Pyrolysis},
volume = {85},
number = {1-2},
pages = {204--213},
publisher = {Elsevier},
abstract = {Acetol (hydroxyacetone) and 1-butanol, model compounds of the aqueous fraction of biomass pyrolysis liquids (bio-oil), have been catalytically steam reformed in a microscale fixed-bed facility. Three Ni coprecipitated catalysts, with varying nickel content (23, 28 and 33% expressed as a Ni/(Ni + Al) relative atomic% of nickel), have been tested. Several parameters have been analysed: the reaction temperature, the catalyst weight/organic flow rate (W/m) ratio, and the effect of the nickel content. The temperatures studied were 550, 650 and 750 °C. At the experimental conditions tested, an increase in the reaction temperature resulted in greater carbon conversion to product gases in non-catalytic and catalytic steam reforming for both model compounds. The nickel content of the catalyst has a significant influence on the steam reforming of oxygenates. The best performance, in terms of H2 yield, is obtained with the catalyst with 28% Ni content. For experiments carried out at space velocities around 30,000 h-1 during 2 h, acetol showed a slightly higher carbon conversion to gas than butanol, though butanol depicted a more constant evolution of carbon conversion throughout. textcopyright 2008 Elsevier B.V. All rights reserved.},
keywords = {},
pubstate = {published},
tppubtype = {article}
}
Acetol (hydroxyacetone) and 1-butanol, model compounds of the aqueous fraction of biomass pyrolysis liquids (bio-oil), have been catalytically steam reformed in a microscale fixed-bed facility. Three Ni coprecipitated catalysts, with varying nickel content (23, 28 and 33% expressed as a Ni/(Ni + Al) relative atomic% of nickel), have been tested. Several parameters have been analysed: the reaction temperature, the catalyst weight/organic flow rate (W/m) ratio, and the effect of the nickel content. The temperatures studied were 550, 650 and 750 °C. At the experimental conditions tested, an increase in the reaction temperature resulted in greater carbon conversion to product gases in non-catalytic and catalytic steam reforming for both model compounds. The nickel content of the catalyst has a significant influence on the steam reforming of oxygenates. The best performance, in terms of H2 yield, is obtained with the catalyst with 28% Ni content. For experiments carried out at space velocities around 30,000 h-1 during 2 h, acetol showed a slightly higher carbon conversion to gas than butanol, though butanol depicted a more constant evolution of carbon conversion throughout. textcopyright 2008 Elsevier B.V. All rights reserved.
Medrano, José A; Oliva, Miriam; Ruiz, Joaquín; García, Lucía; Arauzo, Jesús
Catalytic steam reforming of model compounds of biomass pyrolysis liquids in fluidized bed reactor with modified Ni/Al catalysts Journal Article
In: Journal of Analytical and Applied Pyrolysis, vol. 85, no. 1-2, pp. 214–225, 2009, ISSN: 01652370.
@article{Medrano2009,
title = {Catalytic steam reforming of model compounds of biomass pyrolysis liquids in fluidized bed reactor with modified Ni/Al catalysts},
author = {José A Medrano and Miriam Oliva and Joaquín Ruiz and Lucía García and Jesús Arauzo},
doi = {10.1016/j.jaap.2008.11.025},
issn = {01652370},
year = {2009},
date = {2009-05-01},
journal = {Journal of Analytical and Applied Pyrolysis},
volume = {85},
number = {1-2},
pages = {214--225},
publisher = {Elsevier},
abstract = {Catalytic steam reforming of acetic acid and hydroxyacetone (acetol) as model compounds of the aqueous fraction of bio-oil (biomass derived pyrolysis liquids) was studied in fluidized bed reactor over Ni/Al catalysts modified with calcium or magnesium. Attrition tests showed that the use of small quantities of these promoters improved the mechanical strength of the reforming catalyst. An optimum Ca/Al molar ratio of 0.12 and a Mg/Al molar ratio of 0.26 leaded to attrition rates of 0.22 and 0.27 wt%/h, respectively. Steam reforming experiments were performed at 650 °C and a steam to carbon molar ratio (S/C) of 5.58. The promoted catalysts showed different acetic acid steam reforming activities depending on the Ca/Al or Mg/Al molar ratios. Magnesium modified catalysts with a Mg/Al molar ratios of 0.26 and 0.50 showed good performances with almost no activity loss with time in contrast to the calcium modified catalysts that showed higher CO and CH4 yields. The addition of calcium generated a NiO phase with less interaction with the support. The highest H2 yield and carbon conversion in acetic steam reforming were obtained by a magnesium promoted catalyst with a Mg/Al ratio of 0.26, while the nonpromoted Ni/Al catalyst showed the best performance in acetol steam reforming. Then, the nature of the organic compound influenced the performance of the different catalysts. textcopyright 2008 Elsevier B.V. All rights reserved.},
keywords = {},
pubstate = {published},
tppubtype = {article}
}
Catalytic steam reforming of acetic acid and hydroxyacetone (acetol) as model compounds of the aqueous fraction of bio-oil (biomass derived pyrolysis liquids) was studied in fluidized bed reactor over Ni/Al catalysts modified with calcium or magnesium. Attrition tests showed that the use of small quantities of these promoters improved the mechanical strength of the reforming catalyst. An optimum Ca/Al molar ratio of 0.12 and a Mg/Al molar ratio of 0.26 leaded to attrition rates of 0.22 and 0.27 wt%/h, respectively. Steam reforming experiments were performed at 650 °C and a steam to carbon molar ratio (S/C) of 5.58. The promoted catalysts showed different acetic acid steam reforming activities depending on the Ca/Al or Mg/Al molar ratios. Magnesium modified catalysts with a Mg/Al molar ratios of 0.26 and 0.50 showed good performances with almost no activity loss with time in contrast to the calcium modified catalysts that showed higher CO and CH4 yields. The addition of calcium generated a NiO phase with less interaction with the support. The highest H2 yield and carbon conversion in acetic steam reforming were obtained by a magnesium promoted catalyst with a Mg/Al ratio of 0.26, while the nonpromoted Ni/Al catalyst showed the best performance in acetol steam reforming. Then, the nature of the organic compound influenced the performance of the different catalysts. textcopyright 2008 Elsevier B.V. All rights reserved.
2008
Medrano, José A; Oliva, Miriam; Ruiz, Joaquín; García, Lucía; Arauzo, Jesús
Catalytic steam reforming of acetic acid in a fluidized bed reactor with oxygen addition Journal Article
In: International Journal of Hydrogen Energy, vol. 33, no. 16, pp. 4387–4396, 2008, ISSN: 03603199.
@article{Medrano2008,
title = {Catalytic steam reforming of acetic acid in a fluidized bed reactor with oxygen addition},
author = {José A Medrano and Miriam Oliva and Joaquín Ruiz and Lucía García and Jesús Arauzo},
doi = {10.1016/j.ijhydene.2008.05.023},
issn = {03603199},
year = {2008},
date = {2008-08-01},
journal = {International Journal of Hydrogen Energy},
volume = {33},
number = {16},
pages = {4387--4396},
publisher = {Pergamon},
abstract = {Catalytic steam reforming of bio-oil is a promising process for producing hydrogen in a sustainable environmentally friendly way that can improve the utilization of local resources (natural sources or wastes). However, there remain drawbacks such as coke formation that produce operational problems and deactivation of the catalysts. Coprecipitated Ni/Al catalysts are here used in a fluidized bed for reforming at 650 °C of acetic acid as a model compound of bio-oil-aqueous fraction. Different strategies are applied in order to study their effects on the catalytic steam reforming process: modification of the catalyst by increasing the calcination temperature or adding promoters such as calcium. The addition of small quantities of oxygen is also tested resulting in an optimum percentage to achieve a high carbon conversion process with less coke and without a hydrogen yield penalty production. The results for catalytic steam reforming are compared with other ones from literature. textcopyright 2008 International Association for Hydrogen Energy.},
keywords = {},
pubstate = {published},
tppubtype = {article}
}
Catalytic steam reforming of bio-oil is a promising process for producing hydrogen in a sustainable environmentally friendly way that can improve the utilization of local resources (natural sources or wastes). However, there remain drawbacks such as coke formation that produce operational problems and deactivation of the catalysts. Coprecipitated Ni/Al catalysts are here used in a fluidized bed for reforming at 650 °C of acetic acid as a model compound of bio-oil-aqueous fraction. Different strategies are applied in order to study their effects on the catalytic steam reforming process: modification of the catalyst by increasing the calcination temperature or adding promoters such as calcium. The addition of small quantities of oxygen is also tested resulting in an optimum percentage to achieve a high carbon conversion process with less coke and without a hydrogen yield penalty production. The results for catalytic steam reforming are compared with other ones from literature. textcopyright 2008 International Association for Hydrogen Energy.