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  • Producción de bioaceite e hidrogeno a partir de microalgas mediante procesos de licuefacción hidrotérmica y reformado con vapor en reactores de membrana

    Funding : Ministerio de economía y competitividad (ENE2017-83696-R)
    Start / End Years : 2018 - 2020
    Principal Investigator : Calles Martín, José Antonio y Carrero Fernández, Alicia
    Research Team : - Alique Amor, David - Calles Martín, José Antonio - Carrero Fernández, Alicia - Martínez Díaz, David - Sanz Villanueva, Daniel - Vicente Crespo, Gemma - Vizcaíno Madridejos, Arturo J. 

      Show summary: The controversy generated by the use of agricultural edible crops for energetic applications has increased the interest of microalgae for biofuels production. Microalgae do not need large fields for its cultivation and can grow quickly. Microalgae are a renewable, sustainable and non-polluting feedstock that contribute to reduce the greenhouse gas emissions because they use CO2 in their growth. For these reasons, the overall aim of this project is the sustainable production of hydrogen and bio-oil from microalgae.
      The microalgae hydrothermal liquefaction (HTL) requires lower temperatures than pyrolysis and high pressures to maintain liquid water. This is an advantage because a highly energy demand step like microalgae drying is not needed in liquefaction with the subsequent cost saving. Based on the previous results achieved by the research group (CTQ2013-44447-R project) the bio-oil obtained from one step HTL contains high oxygen (10-20 %) and nitrogen (1-8 %) amounts which are responsible of bio-oil low stability and also of the NOx emissions during bio-oil combustion. To solve these problems, a two-step HTL process is planned in this project. The first step is carried out at low temperature (T< 200 ºC) and provides an aqueous stream by decomposition of proteins and short chain carbohydrates. Next, the solid fraction undergoes a second stage of HTL at higher temperature (T = 250-350°C) with the aim of achieving a bio-oil with low content of nitrogen and oxygen. The second stage of liquefaction also produces a gas stream mainly containing carbon dioxide that may be recirculated to the cultivation of the microalgae.
      The aqueous fractions from both stages of liquefaction can be revalued through the production of high purity hydrogen by catalytic steam reforming in a membrane reactor. Hydrogen can be used as fuel using conventional technologies (combustion engines) or in development ones (fuel cells). Additionally in this project, oxidative steam reforming reactions will be done in order to reduce the energy needs of the process and to avoid catalysts deactivation by coke deposition.
      From the environmental point of view, the project will use tools like the Life Cycle Analysis (LCA) to assess the emissions and energy balances, checking that they conform to a model of sustainable development.






Hydrogen Production through Oxidative Steam Reforming of Acetic Acid over Ni Catalysts Supported on Ceria-Based Materials

Megía, P. J.; Morales, A.; Vizcaíno, A. J.; Calles, J. A.; Carrero, A.

Coke evolution in simulated bio-oil aqueous fraction steam reforming using Co/SBA-15

Megía, P.J.; Vizcaíno, A.J.; Ruiz-Abad, M.; Calles J.A.; Carrero, A.

Pre-activation of SBA-15 intermediate barriers with Pd nuclei to increase thermal and mechanical resistances of pore-plated Pd-membranes

Sanz-Villanueva, D.; Alique, D.; Vizcaíno, A.J.; Sanz, R.; Calles, J.A.

Effect of the incorporation of reducibility promoters (Cu, Ce, Ag) in Co/CaSBA-15 catalysts for acetic acid steam reforming

Megía, P.J.; Calles, J.A.; Carrero, A.; Vizcaíno, A.J.

Stability of electroless pore-plated Pd-membranes in acetic acid steam membrane-reformers for ultra-pure hydrogen production

Adduci, G.; Martinez-Diaz, D.; Sanz-Villanueva, D.; Caravella, A.; Calles, J. A.; Sanz, R.; Alique, D.

Modeling of H2 permeation through electroless pore-plated composite Pd membranes using computational fluid dynamics

Fernández, A.; Casado, C.; Alique, D.; Calles, J.A.; Marugán, J.

Comprehensive permeation analysis and mechanical resistance of electroless pore-plated Pd-membranes with ordered mesoporous ceria as intermediate layer

Martinez-Diaz. D.; Martínez del Monte, D.; García-Rojas, E.; Alique, D.; Calles, J. A.; Sanz, R.

Systematic experimental assessment of concentration polarization and inhibition in Pd-based membranes for hydrogen purification

Tosto, E.; Martinez-Diaz, D.; Sanz, R.; Azzato, G.; Calles, J. A.; Medrano, J. A.; Fernandez, E.; Pacheco Tanaka, D. A.; Gallucci, F.; Alique, D.; Caravella, A.

On the support effect and the Cr promotion of Co based catalysts for the acetic acid steam reforming

Cortese, M.; Ruocco, C.; Palma, V.; Megía, P. J.; Carrero, A.; Calles, J. A.

Hydrogen Production Technologies: From Fossil Fuels toward Renewable Sources. A Mini Review

Megia, P. J.; Vizcaino, A. J.; Calles, J. A.; Carrero, A.

Catalytic behavior of Co-based catalysts in the kinetic study of acetic acid steam reforming

Megía, P.J.; Cortese, M.; Ruocco, C.; Vizcaíno. A.J.; Calles, J.A.; Carrero, A.; Palma, V.

Ultra-pure hydrogen via co-valorization of olive mill wastewater and bioethanol in Pd-membrane reactors

Alique, D.; Bruni, G.; Sanz, R.; Calles, J. A.; Tosti, S.

Agglomerated Co–Cr/SBA-15 catalysts for hydrogen production through acetic acid steam reforming

Calles, J. A.; Carrero, A.; Vizcaíno, A. J.; Megía, P. J.

H2 permeation increase of electroless pore-plated Pd/PSS membranes with CeO2 intermediate barriers

Martínez-Díaz, D.; Sanz, R.; Calles, J. A. Alique, D.

Steam reforming of model bio-oil aqueous fraction using Ni-(Cu, Co, Cr)/SBA-15 catalysts

Calles, J. A.; Carrero, A.; Vizcaíno, A. J.; García-Moreno, L.; Megía, P. J.

Hydrogen production from steam reforming of acetic acid as a model compound of the aqueous fraction of microalgae HTL using Co-M/SBA-15 (M: Cu, Ag, Ce, Cr) catalysts

Megía, P. J.; Carrero, A.; Calles, J. A.; Vizcaíno, A. J.

Pd-thickness reduction in electroless pore-plated membranes by using doped-ceria as interlayer

Martinez-Diaz, D.; Alique, D.; Calles, J.A.; Sanz, R.

Stability of pore-plated membranes for hydrogen production in fluidized-bed membrane reactors

Tosto, E.; Alique, D.; Martinez-Diaz, D.; Sanz, R.; Calles, J.A.; Caravella, A.; Medrano, J.A.; Gallucci, F.

Influence of the selective layer morphology on the permeation properties for Pd-PSS composite membranes prepared by electroless pore-plating: Experimental and modeling study

Calles, J. A.; Sanz, R.; Alique, D.; Furones, L.; Marín, P.; Ordoñez, S.

Review of supported Pd-based membranes prepartation by Electroless Plating for ultra-pure hydrogen production

Alique, D.; Martínez-Díaz, D.; Sanz, R.; Calles, J. A.

Production of Renewable Hydrogen from Glycerol Steam Reforming over Bimetallic Ni-(Cu,Co,Cr) Catalysts Supported on SBA-15 Silica

Carrero, A.; Calles, J.A.; García-Moreno, L.; Vizcaíno, A.J.

Hydrogen production through glycerol steam reforming using Co catalysts supported on SBA-15 doped with Zr, Ce and La

Carrero, A.; Vizcaíno, A. J.; Calles, J. A.; García-Moreno, L.

Comparison of ethanol steam reforming using Co and Ni catalysts supported on SBA-15 modified by Ca and Mg

Vizcaíno, A.J.; Carrero, A.; Calles, J.A.

Effect of Ce and Zr Addition to Ni/SiO2 Catalysts for Hydrogen Production through Ethanol Steam Reforming

Calles, J. A.; Carrero, A.; Vizcaíno, A. J.; Lindo, M.

Hydrogen production in a Pore-Plated Pd-membrane reactor: Experimental analysis and model validation for the Water Gas Shift reaction

Sanz, R.; Calles, J. A.; Alique, D.; Furones, L.; Ordóñez, S.; Marín, P.

Laboratorio virtual: solución de las ecuaciones de conservación mediante volúmenes finitos

Casado, C.; Schiave, E.; Calles, J. A.

  • @tic: revista d'innovaci educativa. Monogrfico: Innovacin Educativa en Ingeniera Qumica, 122-131 (2014)
  • doi:10.7203/attic.13.3905
Thermal stability and effect of typical water gas shift reactant composition on H2 permeability through a Pd-YSZ-PSS composite membrane

Calles, J. A.; Sanz, R.; Alique, D.; Furones, L.

H2 production via water gas shift in a composite Pd membrane reactor prepared by the pore-plating method

Sanz, R.; Calles, J. A.; Alique, D.; Furones, L.

Hydrogen production by glycerol steam reforming over SBA-15-supported nickel catalysts: Effect of alkaline earth promoters on activity and stability

Calles, J. A.; Carrero, A; Vizcaíno, A. J.; García-Moreno, L.

Modelling and simulation of permeation behaviour on Pd/PSS composite membranes prepared by "pore-plating" method

Sanz, R.; Calles, J. A.; Ordóñez, S.; Marín, P.; Alique, D.; Furones, L.

Hydrogen production by steam reforming of ethanol using Ni catalysts based on ternary mixed oxides prepared by coprecipitation

Vizcaíno, A. J.; Lindo, M.; Carrero, A.; Calles, J. A.

Influence of the type of siliceous material used as intermediate layer in the preparation of hydrogen selective palladium composite membranes over a porous stainless steel support

Calles, J. A.; Sanz, R.; Alique, D.

New synthesis method of Pd membranes over tubular PSS supports via "pore-plating" for hydrogen separation processes

Sanz, R.; Calles, J. A.; Alique, D.; Furones, L.

Preparation, testing and modeling of hydrogen selective Pd/YSZ/SS composite membrane

Sanz, R.; Calles, J. A.; Alique, D.; Furones, L.; Ordóñez, S.; Marín, P.; Corengia, P.; Fernández, E.

Effect of Mg and Ca addition on coke deposition over Cu–Ni/SiO2 catalysts for ethanol steam reforming

Carrero, A.; Calles, J.A.; Vizcaíno, A.J.

Influence of hydrocarbon distribution in crude oil and residues on asphaltene stability

Dufuor, J.; Calles, J. A.; Marugán, J.; Giménez-Aguirre, R.; Peña, J. L.; Merino-García, D.

Ethanol steam reforming on Ni/Al-SBA-15 catalysts: Effect of the aluminium content

Lindo, M.; Vizcaíno, A.J.; Calles, J.A.; Carrero, A.

Steam Reforming of Methanol with Sm2O3-CeO2-Supported Palladium Catalysts: Influence of the Thermal Treatments of Catalyst and Support

Gómez-Sainero, L.M.; Baker, R.T.; Vizcaíno, A.J.; Francis, S.M.; Calles, J.A.; Metcalfe, I.S.; Rodríguez, J.J.

Ethanol steam reforming on Mg- and Ca-modified Cu–Ni/SBA-15 catalysts

Vizcaíno, A.J.; Carrero, A.; Calles, J. A.

Ce and La modification of mesoporous Cu–Ni/SBA-15 catalysts for hydrogen production through ethanol steam reforming

Calles, J. A.; Carrero, A.; Vizcaíno, A. J.

Characterization of the asphaltene onset region by focused-beam laser reflectance: a tool for additives screening

Marugán, J.; Calles, J. A.; Dufour, J.; Giménez-Aguirre, R.; Peña, J. L.; Merino-García, D.

Ethanol steam reforming on Ni/Al2O3 catalysts: Effect of Mg addition

Vizcaíno, A. J.; Arena, P; Baronetti, G.; Carrero, A.; Calles, J. A.; Laborde, M. A.; Amadeo, N.

Epoxidation of cyclohexene over basic mixed oxides derived from hydrocalcite materials: Activating agent, solvent and catalyst reutilization

Romero, M. D.; Calles, J. A.; Ocaña, M. A.; Gómez, J. M.

Properties of Asphaltenes Precipitated with Different n-alkanes. A study To Assess the Most Representative Species for Modeling

Calles, J. A.; Dufour, J.; Marugán, J.; Peña, J. L.; Giménez-Aguirre, R.; Merino-García, D.

Hydrogen production by ethanol steam reforming over Cu-Ni supported catalysts

Vizcaíno, A. J.; Carrero, A.; Calles, J. A.

Hydrogen production by ethanol steam reforming over Cu-Ni/SBA-15 supported catalysts prepared by direct synthesis and impregnation

Carrero, A.; Calles, J.A.; Vizcaíno, A.J.

La economía del hidrógeno – una visión global sobre la revolución energética del siglo XXI. 2. Aplicaciones convencionales del hidrógeno y pilas de combustible

San Miguel, G.; Dufour, J.; Calles, J. A.; Botas, J. A.

  • Acta Cientfica y Tecnolgica. Revista de la Asociacin Espaola de Cientficos, 10, 21-27. (2006)
La economía del hidrógeno – una visión global sobre la revolución energética del siglo XXI. 1. Producción y almacenamiento de hidrógeno

Botas, J. A.; Calles, J. A.; Dufour, J.; San Miguel, G.

  • Acta Cientfica y Tecnolgica. Revista de la Asociacin Espaola de Cientficos 9, 33-36 (2005)
Reply to comments by M.Sakuth, S.Sander and J.Gmehling on Chem.Eng.Data,1998, 43, 994-1003

Calleja, G.; Pau, J.; Calles, J.A.

  • J. Chem.Eng.Data, 44,1429-1431 (1999)
Ingeniería de la Industria Alimentaria (vol. 1)

Aguado, J.; Calles, J.A.; Cañizares, P.; López, B.; Rodríguez, F.; Santos, A.; Serrano, D.P.

  • Ed. Sntesis, Madrid (1999)
Pure and Multicomponent Adsorption Equilibrium of Carbon Dioxide, Ethylene and Propane on ZSM-5 Zeolites with different Si/Al Ratios

Calleja, G.; Pau, J.; Calles, J.A.

Prediction of Breakthrough Curves of Phenol Compounds obtained in a Fixed Bed Adsorber of Granular Activated Carbon

Calleja, G.; Rodriguez, J.A.; Calles, J.A.

  • Fundamentals of Adsorption, Engineering Foundation, FOA6, 24-28 (1998)
Hydroconversion of n-decane on bifunctional Ni/HZSM-5 catalysts: effect of zeolite Si/Al ratio and metal loading

Romero, M. D.; Calles, J. A.; Rodríguez, A.; de Lucas, J. A.

  • Anales de Qumica - Internacional, 94(2), 71-77 (1998)
The influence of calcination treatment over bifunctional Ni/HZSM-5 catalysts

Romero, M. D.; Calles, J. A.; Rodríguez, A.; Cabanelas, J. C.

Acidity modification during the agglomeration of ZSM-5 with montmorillonite

Romero, M. D.; Calles, J. A.; Rodríguez, A.; de Lucas, J. A.

  • Microporous Materials, 9(5-6), 221-228 (1997)
Comparison of Molecular Simulation of Adsorption with Experiment

Calleja, G.; Myers, A.L.; Calles, J.A.

  • Adsorption, 3,107-115 (1997)
Influence of the preparation method and metal precursor compound on the bifunctional Ni/HZSM-5 catalysts

Romero, M. D.; Calles, J. A.; Rodríguez, A.

Catalytic Conversion of Polyolefins into Liquid Fuels over MCM-41: Comparison with ZSM-5 and Amorphous SiO2 - Al2O3

Aguado, J.; Sotelo, J. L.; Serrano, D. P.; Calles, J. A.; Escola, J. M.

Bifunctional catalyst Ni/HZSM-5: Effects of the nickel incorporation method

Romero, M. D.; de Lucas, A.; Calles, J. A.; Rodríguez, A.

Thermal deactivation of free and immobilized ß-Glucosidase from Penicillium funiculosum

Aguado, J.; Romero, M. D.; Rodríguez, L.; Calles, J. A.

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