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Prof. Dr. Beatriz Valle
Chemical Engineering Department, University of the Basque Country (UPV/EHU), Spain

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Research Keywords & Expertise

0 Heterogeneous Catalysis
0 Reaction kinetics and mechanisms
0 Valorization of biomass-derived oxygenates
0 H2 production by steam reforming
0 Catalytic conversion of biomass pyrolysis oil into biofuels and value-added chemicals

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H2 production by steam reforming
Catalytic conversion of biomass pyrolysis oil into biofuels and value-added chemicals

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Journal article
Published: 11 June 2021 in Applied Catalysis B: Environmental
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The steam reforming of bio-oil is a promising and economically feasible technology for the sustainable H2 production, yet with the main challenge of designing highly active and stable catalysts. This work aimed to study the deactivation mechanism of a NiAl2O4 spinel derived catalyst, the role of Ni and alumina sites in this mechanism and the appropriate reaction conditions to attenuate deactivation. The reaction tests were carried out in a fluidized bed reactor with prior separation of the pyrolytic lignin. The fresh or used catalysts were characterized using X-ray diffraction, temperature-programmed oxidation, X-ray photoelectron spectroscopy, scanning electron microscopy combined with energy dispersive X-ray spectroscopy, and Raman spectroscopy. For steam/carbon ratios > 3.0, space time above 0.075 h and temperature between 600−700 °C, high initial hydrogen yield is obtained (in the 85–90 % range) with CO yield near 20 %, CH4 yield below 5 % and negligible initial yield of hydrocarbons. The catalyst is more stable at 600 °C, with coke formation preferentially located on Ni sites inside the catalyst particle. Increasing the temperature favors the coke development and consequent deposition on the alumina support, leading to a rapid catalyst deactivation because the limited availability of Ni and alumina sites. These results contribute to understand the phenomenon of catalyst deactivation in the steam reforming of bio-oil and set appropriate reaction conditions to mitigate this problem with a NiAl2O4 spinel derived catalyst.

ACS Style

Naiara García-Gómez; José Valecillos; Aingeru Remiro; Beatriz Valle; Javier Bilbao; Ana G. Gayubo. Effect of reaction conditions on the deactivation by coke of a NiAl2O4 spinel derived catalyst in the steam reforming of bio-oil. Applied Catalysis B: Environmental 2021, 297, 120445 .

AMA Style

Naiara García-Gómez, José Valecillos, Aingeru Remiro, Beatriz Valle, Javier Bilbao, Ana G. Gayubo. Effect of reaction conditions on the deactivation by coke of a NiAl2O4 spinel derived catalyst in the steam reforming of bio-oil. Applied Catalysis B: Environmental. 2021; 297 ():120445.

Chicago/Turabian Style

Naiara García-Gómez; José Valecillos; Aingeru Remiro; Beatriz Valle; Javier Bilbao; Ana G. Gayubo. 2021. "Effect of reaction conditions on the deactivation by coke of a NiAl2O4 spinel derived catalyst in the steam reforming of bio-oil." Applied Catalysis B: Environmental 297, no. : 120445.

Journal article
Published: 13 February 2021 in Fuel Processing Technology
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This work studies the effect that a pre-reforming step (PSR) with low-cost catalyst (dolomite) has on the stability of a Ni-spinel catalyst in the steam reforming (SR) of raw bio-oil. PSR temperature varied in the 400–700 °C range, while SR conditions were kept at 700 °C, space-time = 0.14 gcatalysth/goxygenates, and Steam/Carbon = 3. Deactivated catalysts (characterized by XRD, Raman, TPO, and TEM) showed two types of amorphous coke, whose relative amount depends on the feed composition to SR step, which in turn depends on the prior PSR conditions. Phenols and aromatics (main products of the PSR at 700 °C) favor the formation of coke deposited mainly on Ni sites, whereas non-aromatic oxygenates (major products of the PSR at low temperature) are precursors of coke deposited all over the catalyst surface. PSR at 400 °C leads to low amounts of both coke fractions, enhancing the stability of the Ni spinel catalyst.

ACS Style

Naiara García-Gómez; Beatriz Valle; José Valecillos; Aingeru Remiro; Javier Bilbao; Ana G. Gayubo. Feasibility of online pre-reforming step with dolomite for improving Ni spinel catalyst stability in the steam reforming of raw bio-oil. Fuel Processing Technology 2021, 215, 106769 .

AMA Style

Naiara García-Gómez, Beatriz Valle, José Valecillos, Aingeru Remiro, Javier Bilbao, Ana G. Gayubo. Feasibility of online pre-reforming step with dolomite for improving Ni spinel catalyst stability in the steam reforming of raw bio-oil. Fuel Processing Technology. 2021; 215 ():106769.

Chicago/Turabian Style

Naiara García-Gómez; Beatriz Valle; José Valecillos; Aingeru Remiro; Javier Bilbao; Ana G. Gayubo. 2021. "Feasibility of online pre-reforming step with dolomite for improving Ni spinel catalyst stability in the steam reforming of raw bio-oil." Fuel Processing Technology 215, no. : 106769.

Journal article
Published: 27 December 2019 in Fuel Processing Technology
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The dual role that low-cost dolomite plays as a catalyst and CO2 sorbent in the steam reforming of raw bio-oil has been studied. The reactions were performed in a continuous regime at 700 °C and steam/carbon ratio of 3. The results show that calcined dolomite is a feasible catalyst for producing a H2-rich syngas from raw bio-oil, with efficient CO2 retention and positive impact on the CO2 global emissions balance. Reforming of oxygenates (mainly acids, alcohols and aldehydes) and cracking/hydrogenation of poly-substituted phenols are prevailing reactions during the effective CO2 capture, catalyzed by the CaO and MgO in the dolomite. Consequently, around 40% of bio-oil is converted into a CO2-free syngas with H2 and CO concentrations above 65 vol% and below 20 vol%, respectively, whereas the liquid product is primarily composed of phenol and alkyl-phenols. Products composition changes along reaction by two causes: i) saturation of dolomite by CaO carbonation, which drastically changes the liquid product composition leading to the formation of aromatics by alkyl-phenols hydrodeoxygenation (HDO), activated by the CaCO3 and Fe impurities; ii) coke deposition which involves a progressive decrease in H2/CO ratio (6–2.5 in 4 h) by deactivation of steam reforming and water-gas-shift reactions.

ACS Style

Beatriz Valle; Naiara García-Gómez; Aingeru Remiro; Javier Bilbao; Ana G. Gayubo. Dual catalyst-sorbent role of dolomite in the steam reforming of raw bio-oil for producing H2-rich syngas. Fuel Processing Technology 2019, 200, 106316 .

AMA Style

Beatriz Valle, Naiara García-Gómez, Aingeru Remiro, Javier Bilbao, Ana G. Gayubo. Dual catalyst-sorbent role of dolomite in the steam reforming of raw bio-oil for producing H2-rich syngas. Fuel Processing Technology. 2019; 200 ():106316.

Chicago/Turabian Style

Beatriz Valle; Naiara García-Gómez; Aingeru Remiro; Javier Bilbao; Ana G. Gayubo. 2019. "Dual catalyst-sorbent role of dolomite in the steam reforming of raw bio-oil for producing H2-rich syngas." Fuel Processing Technology 200, no. : 106316.

Journal article
Published: 22 July 2019 in Industrial & Engineering Chemistry Research
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ACS Style

Carolina Montero; Aingeru Remiro; Beatriz Valle; Lide Oar-Arteta; Javier Bilbao; Ana G. Gayubo. Origin and Nature of Coke in Ethanol Steam Reforming and Its Role in Deactivation of Ni/La2O3–αAl2O3 Catalyst. Industrial & Engineering Chemistry Research 2019, 58, 14736 -14751.

AMA Style

Carolina Montero, Aingeru Remiro, Beatriz Valle, Lide Oar-Arteta, Javier Bilbao, Ana G. Gayubo. Origin and Nature of Coke in Ethanol Steam Reforming and Its Role in Deactivation of Ni/La2O3–αAl2O3 Catalyst. Industrial & Engineering Chemistry Research. 2019; 58 (32):14736-14751.

Chicago/Turabian Style

Carolina Montero; Aingeru Remiro; Beatriz Valle; Lide Oar-Arteta; Javier Bilbao; Ana G. Gayubo. 2019. "Origin and Nature of Coke in Ethanol Steam Reforming and Its Role in Deactivation of Ni/La2O3–αAl2O3 Catalyst." Industrial & Engineering Chemistry Research 58, no. 32: 14736-14751.

Journal article
Published: 19 July 2019 in Fuel Processing Technology
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This study deals with a continuous process on a calcined dolomite operating at atmospheric pressure and by co-feeding water for cost-effective upgrading of raw bio-oil at 400 °C and 500 °C. The distribution of carbon in the feed to the product fractions (gas and upgraded bio-oil) and to the dolomite (as CO2 captured and coke) was investigated with time on stream, as well as the evolution of the gas and the upgraded bio-oil composition. Acids and high-molecular weight phenols were completely removed from the raw bio-oil for 0.5 h time on stream, with the upgraded bio-oil being mainly composed of ketones (acetone, 2-butanone and cyclopentanones). Chromatographic analyses of the reaction products were combined with analysis of the dolomite characteristics by thermogravimetry and X-ray diffraction. The results are explained on the basis of possible reaction mechanisms on the dolomite basic sites (CaO, Ca(OH)2 and MgO) and the extent of dolomite carbonation with adsorbed CO2. Composition of the upgraded bio-oil makes it suitable for further catalytic valorization for obtaining fuels and chemicals, such as H2 (by steam reforming) and aromatic hydrocarbons (by dual-stage hydrogenation-cracking processes).

ACS Style

Beatriz Valle; Naiara García-Gómez; Aingeru Remiro; Ana G. Gayubo; Javier Bilbao. Cost-effective upgrading of biomass pyrolysis oil using activated dolomite as a basic catalyst. Fuel Processing Technology 2019, 195, 106142 .

AMA Style

Beatriz Valle, Naiara García-Gómez, Aingeru Remiro, Ana G. Gayubo, Javier Bilbao. Cost-effective upgrading of biomass pyrolysis oil using activated dolomite as a basic catalyst. Fuel Processing Technology. 2019; 195 ():106142.

Chicago/Turabian Style

Beatriz Valle; Naiara García-Gómez; Aingeru Remiro; Ana G. Gayubo; Javier Bilbao. 2019. "Cost-effective upgrading of biomass pyrolysis oil using activated dolomite as a basic catalyst." Fuel Processing Technology 195, no. : 106142.

Journal article
Published: 02 January 2019 in International Journal of Hydrogen Energy
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Alkyl-phenols and hydroxy- or methoxy-phenols (e.g., catechols, guaiacols and syringols) tend to polymerize into carbonaceous structures, causing clogging of reaction equipment and high coke deposition during bio-oil steam reforming (SR). In this work, removal of these phenolic compounds from raw bio-oil was addressed by accelerated aging and liquid-liquid extraction methods. The solvent-anti-solvent extraction with dichloromethane and water was suitable for obtaining a treated bio-oil appropriate for SR. The effect that phenols extraction has on the stability and regenerability of a NiAl2O4 spinel catalyst was studied by conducting reaction-regeneration cycles. Operating conditions were: 700 °C; S/C, 6; space-time, 0.15 gcatalysth/gbio-oil (reaction step), and in situ coke combustion at 850 °C for 4 h (regeneration step). Fresh, deactivated and regenerated catalyst samples were analyzed by temperature programmed oxidation (TPO), temperature programmed reduction (TPR) and X-ray diffraction (XRD). Stability of the Ni-spinel derived catalyst was significantly improved by removing phenols due to attenuation of both coke deposition and Ni sintering. Regenerability of this catalyst was also slightly improved when reforming the treated bio-oil.

ACS Style

Beatriz Valle; Naiara García-Gómez; Aitor Arandia; Aingeru Remiro; Javier Bilbao; Ana G. Gayubo. Effect of phenols extraction on the behavior of Ni-spinel derived catalyst for raw bio-oil steam reforming. International Journal of Hydrogen Energy 2019, 44, 12593 -12603.

AMA Style

Beatriz Valle, Naiara García-Gómez, Aitor Arandia, Aingeru Remiro, Javier Bilbao, Ana G. Gayubo. Effect of phenols extraction on the behavior of Ni-spinel derived catalyst for raw bio-oil steam reforming. International Journal of Hydrogen Energy. 2019; 44 (25):12593-12603.

Chicago/Turabian Style

Beatriz Valle; Naiara García-Gómez; Aitor Arandia; Aingeru Remiro; Javier Bilbao; Ana G. Gayubo. 2019. "Effect of phenols extraction on the behavior of Ni-spinel derived catalyst for raw bio-oil steam reforming." International Journal of Hydrogen Energy 44, no. 25: 12593-12603.

Review
Published: 05 July 2018 in Journal of Chemical Technology & Biotechnology
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Recent advances in lignocellulosic biomass valorization for producing fuels and commodities (olefins and BTX aromatics) are gathered in this paper, with a focus on the conversion of bio‐oil (produced by fast pyrolysis of biomass). The main valorization routes are: (i) conditioning of bio‐oil (by esterification, aldol condensation, ketonization, in situ cracking, and mild hydrodeoxygenation) for its use as a fuel or stable raw material for further catalytic processing; (ii) production of fuels by deep hydrodeoxygenation; (iii) ex situ catalytic cracking (in line) of the volatiles produced in biomass pyrolysis, aimed at the selective production of olefins and aromatics; (iv) cracking of raw bio‐oil in units designed with specific objectives concerning selectivity; and (v) processing in fluidized bed catalytic cracking (FCC) units. This review deals with the technological evolution of these routes, in terms of catalysts, reaction conditions, reactors, and product yields. A study has been carried out on the current state‐of‐knowledge of the technological capacity, advantages and disadvantages of the different routes, as well as on the prospects for the implementation of each route within the scope of the Sustainable Refinery. © 2018 Society of Chemical Industry

ACS Style

Beatriz Valle; Aingeru Remiro; Naiara García-Gómez; Ana G Gayubo; Javier Bilbao. Recent research progress on bio-oil conversion into bio-fuels and raw chemicals: a review. Journal of Chemical Technology & Biotechnology 2018, 94, 670 -689.

AMA Style

Beatriz Valle, Aingeru Remiro, Naiara García-Gómez, Ana G Gayubo, Javier Bilbao. Recent research progress on bio-oil conversion into bio-fuels and raw chemicals: a review. Journal of Chemical Technology & Biotechnology. 2018; 94 (3):670-689.

Chicago/Turabian Style

Beatriz Valle; Aingeru Remiro; Naiara García-Gómez; Ana G Gayubo; Javier Bilbao. 2018. "Recent research progress on bio-oil conversion into bio-fuels and raw chemicals: a review." Journal of Chemical Technology & Biotechnology 94, no. 3: 670-689.

Journal article
Published: 01 March 2018 in Fuel
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ACS Style

Beatriz Valle; Borja Aramburu; Martin Olazar; Javier Bilbao; Ana G. Gayubo. Steam reforming of raw bio-oil over Ni/La2O3-αAl2O3: Influence of temperature on product yields and catalyst deactivation. Fuel 2018, 216, 463 -474.

AMA Style

Beatriz Valle, Borja Aramburu, Martin Olazar, Javier Bilbao, Ana G. Gayubo. Steam reforming of raw bio-oil over Ni/La2O3-αAl2O3: Influence of temperature on product yields and catalyst deactivation. Fuel. 2018; 216 ():463-474.

Chicago/Turabian Style

Beatriz Valle; Borja Aramburu; Martin Olazar; Javier Bilbao; Ana G. Gayubo. 2018. "Steam reforming of raw bio-oil over Ni/La2O3-αAl2O3: Influence of temperature on product yields and catalyst deactivation." Fuel 216, no. : 463-474.

Journal article
Published: 01 March 2018 in Fuel
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ACS Style

Beatriz Valle; Borja Aramburu; Pedro Luis Benito; Javier Bilbao; Ana G. Gayubo. Biomass to hydrogen-rich gas via steam reforming of raw bio-oil over Ni/La2O3-αAl2O3 catalyst: Effect of space-time and steam-to-carbon ratio. Fuel 2018, 216, 445 -455.

AMA Style

Beatriz Valle, Borja Aramburu, Pedro Luis Benito, Javier Bilbao, Ana G. Gayubo. Biomass to hydrogen-rich gas via steam reforming of raw bio-oil over Ni/La2O3-αAl2O3 catalyst: Effect of space-time and steam-to-carbon ratio. Fuel. 2018; 216 ():445-455.

Chicago/Turabian Style

Beatriz Valle; Borja Aramburu; Pedro Luis Benito; Javier Bilbao; Ana G. Gayubo. 2018. "Biomass to hydrogen-rich gas via steam reforming of raw bio-oil over Ni/La2O3-αAl2O3 catalyst: Effect of space-time and steam-to-carbon ratio." Fuel 216, no. : 445-455.

Full paper
Published: 13 February 2018 in ChemCatChem
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The characterization of coke deposited on a Ni/La2O3‐αAl2O3 catalyst used in the steam reforming of bio‐oil has been studied by temperature programmed oxidation (TPO) coupled with different in situ techniques: thermogravimetry (TG), modulated thermogravimetry (MTG), FTIR spectroscopy with mass spectrometry (MS), Raman spectroscopy, and differential scanning calorimetry (DSC). The steam reforming of bio‐oil was carried out in a reactor equipment with two steps in series, comprising bio‐oil thermal treatment (500 °C) and subsequent reforming in a fluidized bed reactor (550–700 °C; and steam‐to‐carbon ratio, 1.5–6). TG/MS‐TPO experiments identify encapsulating and filamentous coke, and a more detailed analysis using other in situ techniques enable to characterize the nature and location of 4 types of coke: (i) an encapsulating coke with aliphatic nature placed in the most superficial layers; (ii) an encapsulating coke with higher aromatic nature in inner layers; (iii) the most superficial layers of a filamentous coke, further from active sites and with a more carbonized structure compared to encapsulating coke; and (iv) an innermost and mainly polyaromatic filamentous coke with a low oxygenates content.

ACS Style

Aitor Ochoa; Beatriz Valle; Daniel E. Resasco; Javier Bilbao; Ana Guadalupe Gayubo; Pedro Castaño. Temperature Programmed Oxidation Coupled with In Situ Techniques Reveal the Nature and Location of Coke Deposited on a Ni/La2 O3 -αAl2 O3 Catalyst in the Steam Reforming of Bio-oil. ChemCatChem 2018, 10, 2311 -2321.

AMA Style

Aitor Ochoa, Beatriz Valle, Daniel E. Resasco, Javier Bilbao, Ana Guadalupe Gayubo, Pedro Castaño. Temperature Programmed Oxidation Coupled with In Situ Techniques Reveal the Nature and Location of Coke Deposited on a Ni/La2 O3 -αAl2 O3 Catalyst in the Steam Reforming of Bio-oil. ChemCatChem. 2018; 10 (10):2311-2321.

Chicago/Turabian Style

Aitor Ochoa; Beatriz Valle; Daniel E. Resasco; Javier Bilbao; Ana Guadalupe Gayubo; Pedro Castaño. 2018. "Temperature Programmed Oxidation Coupled with In Situ Techniques Reveal the Nature and Location of Coke Deposited on a Ni/La2 O3 -αAl2 O3 Catalyst in the Steam Reforming of Bio-oil." ChemCatChem 10, no. 10: 2311-2321.

Research article
Published: 12 January 2018 in Industrial & Engineering Chemistry Research
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The conversion of chloromethane into light olefins over a HZSM-5 zeolite based catalyst is investigated with the aim of establishing a kinetic model suitable for simulating this process for indirect valorization of the methane contained in shale gas. The experimental data were obtained in an isothermal fixed bed reactor under a wide range of operating conditions: temperature, 300-450 ºC; space-time, 1-12 gcatalyst h/molCH2; chloromethane partial pressure, 0.375-1.5 atm, and time on stream, up to 255 min. The reaction scheme is composed of eight components and lumps (chloromethane, C2-C4 olefins, C2-C4 paraffins, C5-C10 aliphatics, aromatics BTX, methane, hydrochloric acid, and chlorinated hydrocarbons), which are involved in ten single reactions. The catalyst deactivation by coke deposition has been quantified by an equation, which is dependent on the concentration of chloromethane in the reaction medium. The kinetic model is suitable for predicting accurately the effect that reaction conditions have on products distribution and their evolution with time on stream.

ACS Style

Mónica Gamero; Beatriz Valle; Ana Guadalupe Gayubo; Pedro Castaño; Andres Tomas Aguayo; Javier Bilbao. Kinetic Model for the Conversion of Chloromethane into Hydrocarbons over a HZSM-5 Zeolite Catalyst. Industrial & Engineering Chemistry Research 2018, 57, 908 -919.

AMA Style

Mónica Gamero, Beatriz Valle, Ana Guadalupe Gayubo, Pedro Castaño, Andres Tomas Aguayo, Javier Bilbao. Kinetic Model for the Conversion of Chloromethane into Hydrocarbons over a HZSM-5 Zeolite Catalyst. Industrial & Engineering Chemistry Research. 2018; 57 (3):908-919.

Chicago/Turabian Style

Mónica Gamero; Beatriz Valle; Ana Guadalupe Gayubo; Pedro Castaño; Andres Tomas Aguayo; Javier Bilbao. 2018. "Kinetic Model for the Conversion of Chloromethane into Hydrocarbons over a HZSM-5 Zeolite Catalyst." Industrial & Engineering Chemistry Research 57, no. 3: 908-919.

Journal article
Published: 01 January 2018 in Chemical Engineering Journal
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ACS Style

Ana G. Gayubo; Beatriz Valle; Borja Aramburu; Carolina Montero; Javier Bilbao. Kinetic model considering catalyst deactivation for the steam reforming of bio-oil over Ni/La2O3-αAl2O3. Chemical Engineering Journal 2018, 332, 192 -204.

AMA Style

Ana G. Gayubo, Beatriz Valle, Borja Aramburu, Carolina Montero, Javier Bilbao. Kinetic model considering catalyst deactivation for the steam reforming of bio-oil over Ni/La2O3-αAl2O3. Chemical Engineering Journal. 2018; 332 ():192-204.

Chicago/Turabian Style

Ana G. Gayubo; Beatriz Valle; Borja Aramburu; Carolina Montero; Javier Bilbao. 2018. "Kinetic model considering catalyst deactivation for the steam reforming of bio-oil over Ni/La2O3-αAl2O3." Chemical Engineering Journal 332, no. : 192-204.

Journals
Published: 14 July 2017 in Green Chemistry
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This work investigates the correlation of the reaction conditions and the reaction medium composition with the deactivation behavior of a Ni/La2O3-αAl2O3 catalyst used in the steam reforming of bio-oil.

ACS Style

Aitor Ochoa; Borja Aramburu; Beatriz Valle; Daniel E. Resasco; Javier Bilbao; Ana G. Gayubo; Pedro Castaño. Role of oxygenates and effect of operating conditions in the deactivation of a Ni supported catalyst during the steam reforming of bio-oil. Green Chemistry 2017, 19, 4315 -4333.

AMA Style

Aitor Ochoa, Borja Aramburu, Beatriz Valle, Daniel E. Resasco, Javier Bilbao, Ana G. Gayubo, Pedro Castaño. Role of oxygenates and effect of operating conditions in the deactivation of a Ni supported catalyst during the steam reforming of bio-oil. Green Chemistry. 2017; 19 (18):4315-4333.

Chicago/Turabian Style

Aitor Ochoa; Borja Aramburu; Beatriz Valle; Daniel E. Resasco; Javier Bilbao; Ana G. Gayubo; Pedro Castaño. 2017. "Role of oxygenates and effect of operating conditions in the deactivation of a Ni supported catalyst during the steam reforming of bio-oil." Green Chemistry 19, no. 18: 4315-4333.

Research article
Published: 19 September 2014 in Energy & Fuels
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Catalytic upgrading was applied to the liquid product obtained from biomass fast pyrolysis (raw bio-oil) in a continuous reaction system by using dolomite as a low-cost catalyst. The upgrading reactor operates at atmospheric pressure without external H2 supply and consists of a thermal treatment section, where pyrolytic lignin is deposited, and a catalytic upgrading section, where the thermally treated oil is valorized in-line. The reaction products, i.e., solid (pyrolytic lignin), gases, and upgraded oil, are collected separately after each reaction. The effect that temperature (400–700 °C) and time on stream (up to 4 h) have on the yield and composition of the products obtained was analyzed for a space-time of 2.4 gdolomite h/gfeed. The dolomite effectively reduced the O/C ratio and removed the carboxylic acids and sugars (mainly levoglucosan) contained in the bio-oil. A gaseous product interesting as a fuel and as raw material for syngas production was obtained below 600 °C, provided that dolomite is not saturated (efficient CO2 capture). Thus, for reaction times of ≈2 h the concentration values in the 400–500 °C range are H2 (5–12%), CO (48–38%), CO2 (2.2–3.2%), and CH4 (23–31%). A good deoxygenation level (≈70%) was achieved after 0.5 h reaction at 600 °C, yielding oil with the O/C ratio ≈ 0.25 and composed of acetone (22%), phenol (51%), and alkyl-substituted phenols (22%). Upgraded oil with low O/C ratio (≈0.21) and high contents of phenol (86.4%) and alkyl-phenols (5.3%) was obtained after 4 h of reaction at 700 °C. This oil has a promising potential for use in phenolic resins formulation and diesel fuel blending.

ACS Style

Beatriz Valle; Borja Aramburu; Claudia Santiviago; Javier Bilbao; Ana G. Gayubo. Upgrading of Bio-Oil in a Continuous Process with Dolomite Catalyst. Energy & Fuels 2014, 28, 6419 -6428.

AMA Style

Beatriz Valle, Borja Aramburu, Claudia Santiviago, Javier Bilbao, Ana G. Gayubo. Upgrading of Bio-Oil in a Continuous Process with Dolomite Catalyst. Energy & Fuels. 2014; 28 (10):6419-6428.

Chicago/Turabian Style

Beatriz Valle; Borja Aramburu; Claudia Santiviago; Javier Bilbao; Ana G. Gayubo. 2014. "Upgrading of Bio-Oil in a Continuous Process with Dolomite Catalyst." Energy & Fuels 28, no. 10: 6419-6428.

Full paper
Published: 23 July 2014 in ChemSusChem
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This work analyses the composition, morphology, and thermal behavior of the carbonaceous materials deposited during the thermal treatment of bio‐oil (thermal pyrolytic lignin—TPL). The bio‐oil was obtained by flash pyrolysis of lignocellulosic biomass (pine sawdust), and the TPLs were obtained in the 400–700 °C range. The TPLs were characterized by performing elemental analysis; 13C NMR, Raman, FTIR, and X‐ray photoelectron spectroscopy; SEM; and temperature‐programmed oxidation analyzed by differential thermogravimetry and differential scanning calorimetry. The results are compared to a commercial lignin (CL). The TPLs have lower oxygen and hydrogen contents and a greater aromaticity and structural order than the CL material. Based on these features, different valorization routes are proposed: the TPL obtained at 500 °C is suitable for use as a fuel, and the TPL obtained at 700 °C has a suitable morphology and composition for use as an adsorbent or catalyst support.

ACS Style

Aitor Ochoa; Borja Aramburu; María Ibáñez; Beatriz Valle; Dr. Javier Bilbao; Dr. Ana G. Gayubo; Pedro Castaño. Compositional Insights and Valorization Pathways for Carbonaceous Material Deposited During Bio-Oil Thermal Treatment. ChemSusChem 2014, 7, 2597 -2608.

AMA Style

Aitor Ochoa, Borja Aramburu, María Ibáñez, Beatriz Valle, Dr. Javier Bilbao, Dr. Ana G. Gayubo, Pedro Castaño. Compositional Insights and Valorization Pathways for Carbonaceous Material Deposited During Bio-Oil Thermal Treatment. ChemSusChem. 2014; 7 (9):2597-2608.

Chicago/Turabian Style

Aitor Ochoa; Borja Aramburu; María Ibáñez; Beatriz Valle; Dr. Javier Bilbao; Dr. Ana G. Gayubo; Pedro Castaño. 2014. "Compositional Insights and Valorization Pathways for Carbonaceous Material Deposited During Bio-Oil Thermal Treatment." ChemSusChem 7, no. 9: 2597-2608.

Short communication
Published: 19 June 2014 in Journal of Cleaner Production
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A study was carried out on the continuous thermal treatment of raw bio-oil and of its aqueous fraction (obtained by adding water) based on the interest of this strategy for separating the pyrolytic lignin, which enhances the valorization of the treated bio-oil in a subsequent in-line catalytic step. It was determined that after the direct thermal treatment of raw bio-oil, 77 wt% oxygenates originally contained in the bio-oil are capable of catalytic valorization, whereas after the treatment of the bio-oil aqueous fraction, 64 wt% of bio-oil oxygenates are amenable to further valorization.

ACS Style

Beatriz Valle; Aingeru Remiro; Borja Aramburu; Javier Bilbao; Ana G. Gayubo. Strategies for maximizing the bio-oil valorization by catalytic transformation. Journal of Cleaner Production 2014, 88, 345 -348.

AMA Style

Beatriz Valle, Aingeru Remiro, Borja Aramburu, Javier Bilbao, Ana G. Gayubo. Strategies for maximizing the bio-oil valorization by catalytic transformation. Journal of Cleaner Production. 2014; 88 ():345-348.

Chicago/Turabian Style

Beatriz Valle; Aingeru Remiro; Borja Aramburu; Javier Bilbao; Ana G. Gayubo. 2014. "Strategies for maximizing the bio-oil valorization by catalytic transformation." Journal of Cleaner Production 88, no. : 345-348.

Journal article
Published: 21 March 2014 in International Journal of Hydrogen Energy
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The feasibility of the steam reforming of bio-oil aqueous fraction and bio-ethanol mixtures has been studied in a continuous process with two in-line steps: thermal step at 300 °C (for the controlled deposition of pyrolytic lignin during the heating of the bio-oil/bio-ethanol feed) followed by steam reforming in a fluidized bed reactor on a Ni/α-Al2O3 catalyst. The effect of bio-ethanol content in the feed has been analyzed in both the thermal and reforming steps, and the suitable range of operating conditions (temperature and space-time) has been determined for obtaining a high and steady hydrogen yield. Higher ethanol content in the mixture feed improves the reaction indices and reduces coke deposition. Operating conditions of 700 °C and space-times higher than 0.23 gcatalyst h (gbio-oil+EtOH)−1 are suitable for attaining almost fully conversion of oxygenates (bio-oil and ethanol) and hydrogen yields above 93%, with low catalyst deactivation.

ACS Style

Aingeru Remiro; Beatriz Valle; Lide Oar-Arteta; Andrés T. Aguayo; Javier Bilbao; Ana G. Gayubo. Hydrogen production by steam reforming of bio-oil/bio-ethanol mixtures in a continuous thermal-catalytic process. International Journal of Hydrogen Energy 2014, 39, 6889 -6898.

AMA Style

Aingeru Remiro, Beatriz Valle, Lide Oar-Arteta, Andrés T. Aguayo, Javier Bilbao, Ana G. Gayubo. Hydrogen production by steam reforming of bio-oil/bio-ethanol mixtures in a continuous thermal-catalytic process. International Journal of Hydrogen Energy. 2014; 39 (13):6889-6898.

Chicago/Turabian Style

Aingeru Remiro; Beatriz Valle; Lide Oar-Arteta; Andrés T. Aguayo; Javier Bilbao; Ana G. Gayubo. 2014. "Hydrogen production by steam reforming of bio-oil/bio-ethanol mixtures in a continuous thermal-catalytic process." International Journal of Hydrogen Energy 39, no. 13: 6889-6898.

Research article
Published: 22 November 2013 in Industrial & Engineering Chemistry Research
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The effect of CO2 capture in hydrogen production by steam reforming of the bio-oil aqueous fraction was studied. The reforming and cracking activity of the adsorbent (dolomite) and the relationship between these reactions and those corresponding to the catalyst (reforming and water gas shift (WGS)) were considered. The experiments were conducted in a two-step system with the first step at 300 °C for pyrolytic lignin retention. The remaining volatiles were reformed in a subsequent fluidized bed reactor on a Ni/La2O3–α-Al2O3 catalyst. A suitable balance was stricken between the reforming and WGS reactions, on the one side, and the cracking and coke formation reactions, on the other side, at 600 °C for catalyst/dolomite mass ratios ≥0.17. At this temperature and space-time of 0.45 gcatalyst h (gbio-oil)−1, bio-oil was fully converted and the H2 yield was around 99% throughout the CO2 capture step. Catalyst deactivation was very low because the cracking hydrocarbon products (coke precursors) were reformed.

ACS Style

Aingeru Remiro; Beatriz Valle; Borja Aramburu; Andrés T. Aguayo; Javier Bilbao; Ana G. Gayubo. Steam Reforming of the Bio-Oil Aqueous Fraction in a Fluidized Bed Reactor with in Situ CO2 Capture. Industrial & Engineering Chemistry Research 2013, 52, 17087 -17098.

AMA Style

Aingeru Remiro, Beatriz Valle, Borja Aramburu, Andrés T. Aguayo, Javier Bilbao, Ana G. Gayubo. Steam Reforming of the Bio-Oil Aqueous Fraction in a Fluidized Bed Reactor with in Situ CO2 Capture. Industrial & Engineering Chemistry Research. 2013; 52 (48):17087-17098.

Chicago/Turabian Style

Aingeru Remiro; Beatriz Valle; Borja Aramburu; Andrés T. Aguayo; Javier Bilbao; Ana G. Gayubo. 2013. "Steam Reforming of the Bio-Oil Aqueous Fraction in a Fluidized Bed Reactor with in Situ CO2 Capture." Industrial & Engineering Chemistry Research 52, no. 48: 17087-17098.

Research article
Published: 21 November 2013 in Energy & Fuels
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ACS Style

Aingeru Remiro; Beatriz Valle; A. T. Aguayo; Javier Bilbao; Ana G. Gayubo. Steam Reforming of Raw Bio-oil in a Fluidized Bed Reactor with Prior Separation of Pyrolytic Lignin. Energy & Fuels 2013, 27, 7549 -7559.

AMA Style

Aingeru Remiro, Beatriz Valle, A. T. Aguayo, Javier Bilbao, Ana G. Gayubo. Steam Reforming of Raw Bio-oil in a Fluidized Bed Reactor with Prior Separation of Pyrolytic Lignin. Energy & Fuels. 2013; 27 (12):7549-7559.

Chicago/Turabian Style

Aingeru Remiro; Beatriz Valle; A. T. Aguayo; Javier Bilbao; Ana G. Gayubo. 2013. "Steam Reforming of Raw Bio-oil in a Fluidized Bed Reactor with Prior Separation of Pyrolytic Lignin." Energy & Fuels 27, no. 12: 7549-7559.

Journal article
Published: 25 September 2013 in Applied Catalysis B: Environmental
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The influence of calcination and reduction temperatures of Ni/La2O3–αAl2O3 catalyst used in the steam reforming of raw bio-oil was studied in the 550–850 °C range. The experiments were conducted by continuously feeding a mixture of raw bio-oil/ethanol (20 wt% of ethanol) in a two-step system: the first for thermal treatment of bio-oil at 500 °C, with pyrolytic lignin separation, and the second for the steam reforming of volatiles in a fluidized bed catalytic reactor at 700 °C. The properties of the catalysts were analyzed by N2 adsorption–desorption, hydrogen chemisorption, inductively coupled plasma atomic emission mass spectroscopy (Q-ICP-MS), X-ray diffraction spectroscopy (XRD) and temperature programmed reduction (TPR). The coke deposited on the deactivated catalysts was quantified by temperature programmed oxidation (TPO). Both calcination and reduction temperatures have a significant effect on the amount and nature of the active metal dispersed on the support and they play an important role on the activity and stability of the catalyst throughout the reforming reaction. The catalyst calcined at 550 °C and reduced at 700 °C yielded the highest values of bio-oil conversion and hydrogen yield and were the most stable of the tested catalysts over 4 h reaction.

ACS Style

Beatriz Valle; Borja Aramburu; Aingeru Remiro; Javier Bilbao; Ana G. Gayubo. Effect of calcination/reduction conditions of Ni/La2O3–αAl2O3 catalyst on its activity and stability for hydrogen production by steam reforming of raw bio-oil/ethanol. Applied Catalysis B: Environmental 2013, 147, 402 -410.

AMA Style

Beatriz Valle, Borja Aramburu, Aingeru Remiro, Javier Bilbao, Ana G. Gayubo. Effect of calcination/reduction conditions of Ni/La2O3–αAl2O3 catalyst on its activity and stability for hydrogen production by steam reforming of raw bio-oil/ethanol. Applied Catalysis B: Environmental. 2013; 147 ():402-410.

Chicago/Turabian Style

Beatriz Valle; Borja Aramburu; Aingeru Remiro; Javier Bilbao; Ana G. Gayubo. 2013. "Effect of calcination/reduction conditions of Ni/La2O3–αAl2O3 catalyst on its activity and stability for hydrogen production by steam reforming of raw bio-oil/ethanol." Applied Catalysis B: Environmental 147, no. : 402-410.