Tomas Ramirez Reina

Dr Tomas Ramirez Reina


Senior Lecturer / Director of Employability
MChem, MSc, PhD, AMIChemE, FHEA
+44 (0)1483 686597
30 BC 02
Moday to Friday 9am to 5pm

Academic and research departments

Department of Chemical and Process Engineering.

Biography

Biography

 

Dr. Reina specialises in heterogeneous catalysis for energy and sustainability. His research interests are focused on the application of engineered catalysts to different fuel processing technologies to enable the transition from fossil to renewable fuels. Currently, he is leading The Catalysis Unit at the Chemical and Process Engineering Department. His team is developing innovative catalysts and green catalytic processes with potential impact on the hydrogen economy and the next generation of biofuels. Additionally, their investigations towards efficient routes for CO2 conversion into fuels and platform chemicals has been featured by the scientific community (see further info at "in the media" section)

Career history

2019-Present: Senior Lecturer. Department of Chemical and Process Engineering, Faculty of Engineering and Physical Sciences, University of Surrey.

2016-2019: Lecturer. Department of Chemical and Process Engineering, Faculty of Engineering and Physical Sciences, University of Surrey.

2014-2016: Research Associate, Chemical Engineering Department, Imperial College London, UK.

September 2012-December 2012: Visiting Researcher, FORHT-Institute of Chemical Engineering and High Temperature processes (ICE-HT), Patras, Greece.

July 2012: Visiting Researcher, Institute of Catalysis, Bulgarian Academy of Sciences, Sofia, Bulgaria.

September 2011-December 2011: Visiting Researcher, Brookhaven National Laboratory (BNL) New York, USA.

2010-2014: PhD project. Materials Science Institute of Seville, Seville, Spain.

Past Projects Involved

- Bimetallic gold nanoparticles for CO abatement reactions, Sponsored by Spanish Council of Scientific Research CSIC (2010-2014)

- CO2 utilization for syngas production, Sponsored by Junta de Andalucía (2012-2014) P11-TEP-8196

- Design and characterization of gold based catalysts for pure hydrogen production for fuel cell applications, sponsored by Spanish Council of Scientific Research, CSIC and the Bulgarian Academy of Sciences, BAS (2011-2012)

- Microchannel reactors for GTL processes, Sponsored by Spanish Ministry of Economy (2012-2014) ENE2012-37431-C03-01.

- Energy efficient heat exchange and catalysis: UNIHEAT (Imperial College London and Boreskov Institute of Catalysis) Sponsored by BP and Skolkovo Foundation (2014-2016)

- Graded membranes for energy efficient new generation carbon capture process (GREEN-CC) FP7 project sponsored by European Union (2014-2016)

- Partial oxidation of methane to methanol (Imperial College London-Shell)

 

Current Research Grants

EPSRC - Global Challenges Research Fund: “Catalytic Solutions to Mitigate Global Warming in Latin America”

Newton-Paulet Fund Researcher Links "Sustainable Biomass Processing and Conversion"

Royal Society Research Grant: "Engineering Solutions for CO2 Conversion" 

EPSRC - CO2Chem UK seedcorn grant: “CATBIO-HYDROGEN”

University of Surrey RIS innovation project: "Catalytic Membranes for Green House Gases Abatement" 

British Council Institutional Links UK-Argentina: BIOGAS-TECH

EPSRC Surrey IAA: "Power to Gas using advanced catalytic membranes"

SPRINT - SPace Research and Innovation Network for Technology: "Micro-catalytic reactors for mono-propellant thrusters in small satellites" 

EPSRC Surrey IAA: "Application of Natural Materials as Catalytic and/or Support Materials for Environmentally Benign Processes"

Research interests

- Catalysis for Energy and Sustainability

- Heterogeneous catalysis & Reaction Engineering

- Oxidation catalysis

- New Catalytic Materials and Nano-Sized Catalysts

- Hydrogen production for fuel cells

- Efficient routes for CO2 conversion

- Heavy oil upgrading

- Catalysis in Supercritical Fluids

- Catalytic biomass valorisation

Research collaborations

Imperial College London (London, UK), University of Seville (Seville, Spain), Institute of Catalysis, Bulgarian Academy of Sciences (BAS) (Sofia, Bulgaria), Brookhaven National Laboratory (BNL) (New York, USA), Institute of Chemical Engineering (ICE-HT, Patras Greece), Advanced Materials Laboratory (Alicante, Spain), Boreskov Institute of Catalysis (Novosibirsk, Russia), University of Cadiz (Cadiz, Spain), University of Oxford (UK), University of Bath (UK), Universidad Nacional de Colombia (Bogota, Colombia), INTI (Buenos Aires, Argentina), Universidad de Boyaca (Colombia), Universidad de Antioquia (Medellin, Colombia), Queen Mary University London (UK), Advanced Technology Institute (Surrey, UK), Cardiff Institute of Catalysis (Cardiff, UK), KBR, Heriot-Watt University (Scotland, UK), ECUST (China), HUST (China), Dalian Institute of Chemical Physics (China), Beijing Forestry University (China)

Teaching

Design Projects ENG3192

Chemical Reaction Engineering ENG2113 (module coordinator)

Supervision of MEng Research Projects ENGM276

Supervision of MSc Research Dissertation Projects ENGM083

Departmental duties

Erasmus Coordinator / Faculty Mobility Leader 

Academic Responsible of the Energy and Reaction Engineering Lab

Head of the Catalysis Unit

Member of the Teaching Committee - Year 2 academic rep.

Member of the Vice-Chancellor’s Academic Consultative Ensemble (VC-ACE)

Co-Coordinator of the Energy & Materials Research Centre 

 

Affiliations

Visiting Professor HUST University China

Fellow of the Spanish Society of Catalysis, SECAT

Associate editor Frontiers in Chemistry

Associate editor Frontiers in Chemical Engineering

Editor of Chemistry - MDPI

Guess Editor of Catalysts - MDPI

EPSRC Peer Review College

Associate Member of the IChemE

Fellow of the Higher Education Academy 

SPRINT board of Experts 

Other activities

External PhD Examiner  for the Inorganic Chemistry Department at Oxford University (UK), University of Queensland (Australia) Materials Science Institute of Seville (Spain),  National Institute of Carbon (Zaragoza, Spain), School of Chemical Engineering (Seville, Spain), Institute of Advanced Materials -University of Alicante (Alicante, Spain)  Chemical Engineering Department at University of Antioquia (Colombia), National University of Colombia (Colombia). 

External Projects Reviewer for the Polish Physical Sciences and Engineering Research Council

Panel member of the Research Foundation – Flanders (FWO

Projects Reviewer for ACS Petroleum Research Fund

 

Selected Conferences Contributions

1. H. Arellano-Garcia, E. Ketabchi, T.R. Reina “Integration of Biorefinery Concepts in Oil Refineries” ESCAPE-27 Barcelona (Spain) 2017.

2. E. le Saché, Y. Peng, H. Arellano-Garcia, T.R. Reina, “Model-Based Analysis and Integration of Synthetic Methane Production and Methane Oxidative Coupling

ESCAPE-27 Barcelona (Spain) 2017.

3 .E. Le Sache, H. Arellano-Garcia, D. Watson, T.R. Reina “Integrated Reactor Design and Catalysts Development for an efficient CO2 conversion via dry reforming

10th World Conference on Chemical Engineering, Barcelona (Spain) 2017

4. R. Volpe 1, J.M. Bermúdez, T.R. Reina, M. Millan-Agorio “Reaction pathways among products of agro- waste thermochemical breakdown”

10th World Conference on Chemical Engineering, Barcelona (Spain) 2017

5. E. le Saché, L. Pastor-Pérez, D. Watson, A. Sepúlveda-Escribano, T.R. Reina “Highly active and stable Ni based crystalline oxide catalyst for methane dry reforming”

Europacat 2017 Florence (Italy)

6. L. Pastor-Pérez, C. Price, E. le Saché, A. Sepúlveda-Escribano and T.R. Reina “Could we overcome the space velocity limitations of Cu-ZnO catalysts for the WGS reaction?

Europacat 2017 Florence (Italy)

7. L. Pastor-Pérez, T.R. Reina, A. Sepulveda-Escribano “On the cooperative effect of Cu-Ni in multicomponent Ni-Cu catalysts for the WGS reaction”

Spanish conference on Catalysts, Oviedo, Spain, June 2017

8. U. Guharoy, Q. Cai, T. R. Reina, S. Gu “DFT Study of Dry (CO2) Reforming of Methane over Sn-Doped Ni(111) Surface”

ChemEngDayUK, University of Birmingham, UK, March 2017

9 U. Guharoy, Q. Cai, T. R. Reina, S. Gu “Effect of Sn surface alloying with Ni (111) on increased carbon tolerance in dry (CO2) reforming of methane to syngas : A DFT study”

4th energy materials symposium University of Bath, September 2017

10. S. Pirou, J.M. Bermúdez, B. Tak Nac, J.H. Yuc, P. V. Hendriksen, A. Kaiser, T.R. Reina, M. Millan and R. Kiebach “Stability and Performance of Robust (ZrO2)0.89(Y2O3)0.01(Sc2O3)0.10 LaCr0.85Cu0.10Ni0.05O3-δ Oxygen Transport Membranes”

15th International Conference on Inorganic Membranes, Dresden, Germany, June 2017

11. T.R. Reina, H. Arellano-Garcia “Development of novel catalysts and reactor configurations for methane dry reforming”

AlChE annual meeting (2016) San Francisco, USA, November 2016

12. T.R. Reina, P. Yeletski , J. M. Bermudez , P. Arcelus-Arrillaga , V.A. Yakovlev , M. Millan “Polycyclic hydrocarbons upgrading using NiMo/SiO2 catalysts in supercritical water conditions”

Iberoamerican conference on Catalysis (CICAT 2016) Montevideo, Uruguay, September 2016

13. T.R. Reina, L. Pastor-Perez, J.M. Bermudez, A. Sepulveda Escribano, M. Millan “Advanced catalysts for hydrocracking reactions: the multiple role of Cr as NiMo/Al2O3 promoter”

Iberoamerican conference on Catalysis (CICAT 2016) Montevideo, Uruguay, September 2016

14. T.R. Reina, H. Arellano-Garcia “Emissions to liquid fuels via methane dry reforming”

ChemReactor 22, London, UK, September 2016.

15. T.R. Reina, H. Arellano-Garcia “Engineering solutions for CO2 conversion: Emissions to fuels and chemicals”

Process System Engineering day, London, UK, July 2016.

16. J.M Bermudez, J. Garcia-Fayos, T.R Reina, G. Reed, M. Millan-Agorio, J. M Serra “Thermochemical stability of NiFe2O4-Ce0.8Tb0.2O2-δ under real conditions for its application in 4-end module oxygen transport membranes for oxycombustion”

14th International Conference on Inorganic Membranes, Atlanta, USA, July 2016

17. R. Volpe, J.M. Bermúdez, T.R. Reina, M. Millan-Agorio “Reactivity of chars from the pyrolysis of citrus pulp: chemical, structural and thermal characterization”

The UK-Malaysia workshop on Bioenergy, Biorefinery and Bioeconomy, Kuala Lumpur Malasya May 2016.

18. C.Heide, T.R.Reina, M.Millan, “Phenanthrene hydrocracking using a Cr-doped NiMo/Al catalyst: Effect of the operating conditions and approach to the reaction pathway” Lightning Poster Session

19.T.R. Reina, P. Yeletski , J. M. Bermudez , P. Arcelus-Arrillaga , V.A. Yakovlev , M. Millan “Partial oxidation of Anthracene using NiMo/SiO2 catalysts in supercritical water conditions”

AlChE annual meeting (2015) Salt Lake City, USA, November 2015.

20. M.González-Castaño, T.R.Reina, V. López-Flores, S.Ivanova, L.M. Martínez, J.A. Odriozola “Noble metal/ceria catalysts for the WGS reaction. Why gold and platinum behave differently? “

AlChE annual meeting (2015) Salt Lake City, USA, November 2015

21.J.L. Santos, T.R. Reina, I.Ivanov, S. Ivanova, T. Tabakova, M.A. Centeno, V.Idakiev, J. A.Odriozola “Gold modified hydrotalcite Cu/ZnO/Al2O3 catalysts for pure hydrogen production”

11th International Symposium on Heterogeneous Catalysis, Varna Bulgaria, September 2015

22. M. González, T.R.Reina, S. Ivanova, M.A.Centeno, J.A. Odriozola “O2-assisted Water Gas Shift reaction using Au and Pt structured catalysts"

Spanish conference on Catalysts, Barcelona, Spain, July 2015

23. T.R.Reina, M. González, S. Ivanova, M.A. Centeno, J.A. Odriozola “Unrevealing the mechanism of the WGS reaction over Au/CeO2-FeOx/Al2O3 catalysts”

AlChE annual meeting (2014) Atlanta, USA, November 2014.

24. T.R. Reina, S.Ivanova, M.A. Centeno J.A. Odriozola “Viability of Au/CeO2-CuO/Al2O3 catalysts for pure hydrogen production via the Water-Gas Shift reaction”

Iberoamerican conference on Catalysis (CICAT 2014) Medellin, Colombia, September 2014.

25. O. Arbelaez, T.R. Reina, S.Ivanova, F. Bustamente, M.A. Centeno, J. A. Odriozola “Mono and bimetallic Cu-Ni structured catalysts for the water gas shift reaction”

Iberoamerican conference on Catalysis (CICAT 2014) Medellin, Colombia, September 2014.

26.T.R. Reina, S. Ivanova, M.A. Centeno, J.A. Odriozola “Boosting the activity of a Au/CeO2/Al2O3 catalysts for the WGS reaction”

Fundatamentals and applications of cerium dioxe in catalysis. Udine, Italy July 2014.

27. I. Ivanov, T.R. Reina, S. Ivanova, T. Tabakova, M.A. Centeno, J.A. Odriozola V. Idakiev “copper based layered double hydroxides as catalysts for the water gas shift reaction”

Bulgarian National conference on chemistry (2014) Sofia, Bulgaria, June 2014

28. T.R. Reina, E. Papadopoulou, S. Ivanova, M.A. Centeno, T. Ioannides J. A. Odriozola “Could an excellent WGS catalyst be useful in the PROX reaction?” talk awarded with the EFCATS award.

European Congress on Catalysis (EuropaCat13) Lyon, France, September 2013.

29. M.González, T.R. Reina, S. Ivanova, M.A. Centeno, J.A. Odriozola “Pt vs Au for the WGS, could Pt take the gold? “ European Congress on Catalysis (EuropaCat13) Lyon, France, September 2013.

30. T.R. Reina, A. Pérez, S. Ivanova, M.A. Centeno, J.A. Odriozola “H2 oxidation as a criteria for a PrOx catalyst selection”

World Congress on Oxidation Catalysis (WCOC) Saint Louis, Missouri, USA, June 2013.

31. Spanish conference on Catalysts, Sevilla, Spain, June 2013 organizing committee

32. M. González, T. R. Reina, S. Ivanova, M.A.Centeno, J. A. Odriozola “Pt vs Au en WGS

Spanish conference on Catalysts, Sevilla, Spain, June 2013”

33. T.R. Reina, A. Pérez, S. Ivanova, M.A. Centeno, J.A. Odriozola “PrOx reaction over Au/CeO2-ZnO/Al2O3 catalysts”

Spanish conference on Catalysts, Sevilla, Spain, June 2013.

34. T.R.Reina, S. Ivanova, M. A. Centeno, J. A. Odriozola “WGS and “PrOx: two reactions, one single catalyst”

Spanish conference on Catalysts, Sevilla, Spain, June 2013.

35. M. Espitia, T.R.Reina, M. A. Centeno, J. A. Odriozola, S. Moreno, R. Molina “Ce-promoted Cobalt catalysts for oxidative ethanol reforming: effect of the WGS in the CO conversion”

Spanish conference on Catalysts, Sevilla, Spain, June 2013.

36. T.R. Reina, W. Xu , S. Ivanova, M.A. Centeno, J. Hanson , J.A. Rodriguez , J.A. Odriozola “Operando characterisation of Au/CeO2-Fe2O3/Al2O3 during the WGS reaction”

Iberoamerican conference on Catalysis (CICAT 2012) Santa Fe, Argentina, September 2012.

37. T.R. Reina, S. Ivanova, V. Idakiev, T. Tabakova, M.A. Centeno, J. A. Odriozola “Economically viable highly active gold based catalyst for WGSR”

15th International Congress on Catalysis (ICC 2012) Munich, Germany, July 2012.

38. T.R. Reina, W. Xu, S. Ivanova, M.A. Centeno, J. Hanson , J.A. Rodriguez , J.A. Odriozola “Operando characterization of iron-promoted ceria-alumina gold catalysts during the water-gas shift reaction

IV Operando Spectroscopy, Brookhaven National Laboratory, Upton, New York, USA, April 2012

39. T.R. Reina, S. Ivanova,V. Idakiev, T. Tabakova, M. A.Centeno, J. A. Odriozola “Gold supported on transition metal-doped ceria-catalysts for CO oxidation

European conference on catalysis EUROPACAT 11, Glasgow, Scotland, July 2011

40. T.R. Reina, S. Ivanova, A. Corrales, M.A Centeno, J.A. Odriozola “CO oxidation over Au/ZnO/ CeO2-Al2O3 catalysts“ Spanish conference on Catalysts, Zaragoza, Spain, June 2011

 

Invited Talks

1. Tomas Ramirez Reina “Design and Characterization of gold based catalysts for the water gas shift reaction

Keynote at the Spanish Conference on Catalysis, Barcelona, Spain July 2015.

2. Tomas Ramirez Reina “Advanced oxidation reactions for sustainable energy

Keynote Catalysis Doctoral Centre - University of Bath, UK, May 2017.

3. Tomas Ramirez Reina “Design of advanced catalysts for clean hydrogen production

Keynote 7th KACST-Oxford Petrochemical Forum 2017, The Royal Society, London, June 2017.

4. Tomas Ramirez Reina “Engineering Solutions for Global Challenges

Keynote INTI-University of Surrey workshop, Buenos Aires, Argentina, September 2017.

5. Tomas Ramirez Reina “Catalysis in the context of Global Challenges”

Plenary lecture East China University of Science and Technology, Shanghai, China November 2017.

6.Tomas Ramirez Reina “Advanced Catalysts for Energy and CO2 conversion applications”

Plenary lecture Zhengzhou University, Zhengzhou, China November 2017

7. Tomas Ramirez Reina “Conversion of Bioresources using carbon based catalysts”

Keynote University of Piura, Peru June 2018.

8. Tomas Ramirez Reina “Multicomponent catalysts for the Global Challenges”

Keynote Catalysis Doctoral Centre – University of Cardiff, UK, June 2018

9. E. Le Sache, T. R. ReinaNi stabilised in La2Zr2O7: superior catalyst for gas-phase CO2 recycling”

Invited talk – CO2Chem UK Status Conference – awarded seedcorn grant presentation. Loughborough University, September 2018

10. T.R.Reina “ Catalytic Systems to Address Energy Challenges”

Invited seminar – Research Centre for Carbon Solutions – Heriot-Watt University, Scotland November 2018.

11. T.R.Reina  "Advanced Catalysts for a Low Carbon Future"

Invited Lecture - Beijing Forestry University (China), October 2019

12. T.R. Reina "Engineering Catalysts for gas phase CO2 conversion"

Distinguished Webinar - Iberoamerican University, Mexico City, May 2020. 

 

Awards and distinctions

1. Best PhD thesis in the field of catalysis 2014 by the Spanish Catalysis Society (SECAT).

2. Extraordinary PhD award University of Seville 2013/2014.

3. European Federation of Catalysis (EFCATS) student award 2013.

4. Finalist for the Best PhD thesis in the field of catalysis in Europe 2013-2014 (EFCATS)

5. Featured article selected by editor in chief of the Journal of Catalysis (June 2015)

6. Supervised project awarded: 2015 Prize for Best Performance in an MSc Research Project. Chemical Engineering Department, Imperial College London.

7. Nominated for Student Academic Choice Award for Best Supervision while working in the Chemical Engineering Department at Imperial College London (2015)

8. Finalist for the IChemE awards 2016 “Young Academic Researcher”

9. Finalist for the IChemE awards 2017 “Young Academic Researcher”

10. Staff Award for Outstanding University Talent - University of Surrey 2017.

11. Young Scientist award 2017 by Seville City Council

12. Royal Academy of Sciences - Royal Cavalry Armory of Seville, Young Scientist award 2018

13. Faculty of Engineering and Physical Sciences - Teacher of the Year Award - 2019

Publication highlights

  1. T.R. Reina, S. Ivanova, M.I. Domínguez, M.A. Centeno, J.A. Odriozola. "Sub-ambient CO oxidation over Au/MOx/CeO2-Al2O3 (M=Zn or Fe)" Applied Catalysis A: General 419-420 (2012) 58-66.
  2. T.R. Reina, S. Ivanova, A. Alvarez, M.A. Centeno, J. A. Odriozola. "Influence of the transition metal oxide presence on the CO oxidation behavior of Au/MOx/CeO2-Al2O3 systems (M=V or Co)ChemCatChem 4 (2012) 512-520.
  3. T.R. Reina, W. Xu, S. Ivanova, M. A. Centeno, J. Hanson, J. A. Rodriguez, J.A. Odriozola. "In situ characterization of iron-promoted ceria-alumina gold catalysts during the water-gas shift reaction" Catalysis Today 205 (2013) 41-48.
  4. T.R. Reina, S. Ivanova, V. Idakiev, J. J. Delgado, I. Ivanov, T. Tabakova, M.A. Centeno, J.A. Odriozola "Impact of Ce-Fe synergism on the catalytic behaviour of Au/CeO2-FeOx/Al2O3 for pure H2 production" Catalysis Science and Technology 3 (3) (2013) 779-787.
  5. T.R. Reina, A. Alvarez, S. Palma, S. Ivanova, F. Romero-Sarria, M.A. Centeno, J.A. Odriozola. "Influence of the lanthanide oxides on the catalytic behavior of Au/Al2O3 catalysts for total and preferential CO oxidation" Advanced Chemistry Letters 1 (2013) 237-246.
  6. T.R. Reina, S. Ivanova, M.A. Centeno, J.A. Odriozola, "Low Temperature CO oxidation on multicomponent gold based systems" Frontiers in Chemistry 1 (2013) 12.
  7. T. R. Reina, E. Papadopoulou, S.Palma, S. Ivanova, M.A Centeno, T. Ioannides, J.A. Odriozola. "Could an efcient WGS catalyst be useful in the CO-PrOx reaction?" Applied Catalysis B: Env. 150-151 (2014) 554-563.
  8. T.R. Reina, S. Ivanova, J.J. Delgado, I. Ivanov, T. Tabakova, V. Idakiev , M.A. Centeno, J. A. Odriozola "Viabilty of Au/CeO2-ZnO/Al2O3 catalysts for pure hydrogen production by the Water-Gas Shift reaction" ChemCatChem 6 (2014) 1401 – 1409.
  9. M. González, T.R. Reina, S. Ivanova, M.A. Centeno, J.A. Odriozola "Pt vs Au in WGS reaction" Journal of Catalysis (2014) 314, 1-9.
  10. T.R. Reina, M. González, S. Ivanova, M.A. Centeno, J.A. Odriozola “Unrevealing the mechanism of the WGS reaction over Au/CeO2-FeOx/Al2O3 catalysts" AlChE 2014 conference paper vol. 1 (2014) 498499. ISBN 978-151081252-9.
  11. T.R. Reina, S. Ivanova, M.A. Centeno, J.A. Odriozola "Catalytic screening of Au/CeO2MOx/Al2O3 catalysts (M= La,Ni,Cu,Fe,Cr,Y) in the CO-PrOx reaction" International Journal of Hydrogen Energy 40 (2015) 1782-1788.
  12. T.R. Reina, S. Ivanova, M.A. Centeno, J. A. Odriozola "Boosting the activity of a Au/CeO2/Al2O3 catalysts for the WGS reaction" Catalysis Today 253 (2015) 149-154.
  13. T.R. Reina, C.Megia-Sayago, A.Perez-Florez, S.Ivanova, M.A. Centeno, J.A. Odriozola “H2 oxidation as criterion for PrOx catalyst selection: Examples based on Au–CoOx-supported systems” Journal of Catalysis 326 (2015) 161-171.
  14. T.R. Reina, P. Yeletski, J.M. Bermudez , P. Arcelus-Arrillaga, V. A. Yakovlev, M.Millan “Partial oxidation of anthracene using NiMo/SiO2 catalysts in supercritical water conditions” AlChE 2015 conference paper vol. 1 (2015) 559-565. ISBN 978-151081853-8
  15. O. Arbelaez, T.R. Reina, S. Ivanova, F. Bustamente, M. A. Centeno, J.A. Odriozola “Mono and bimetallic Cu-Ni structured catalysts for the water gas shift reactionApplied Catalysis A: Gen. 497 (2015) 1-9.
  16. L. Pastor-Perez, T.R. Reina, S. Ivanova, M.A. Centeno, A. Sepulveda, J.A. Odriozola “Ni/CeO2/C catalysts with enhanced OSC for the WGS reactionCatalysts 5 (1) (2015) 298-309.
  17. M. González, T.R. Reina, S. Ivanova, M.A. Centeno, J.A. Odriozola “O2-assisted Water Gas Shift reaction using Au and Pt structured catalysts" Applied Catalysis B: Env. 185 (2016) 337-343.
  18. T.R. Reina, S. Ivanova, V. Idakiev, T. Tabakova, M. A. Centeno, Q.-F. Deng, Z.-Y. Yuan, J.A. Odriozola“Nanogold mesoporous iron promoted ceria catalysts for total and preferential CO oxidation reactionsJournal of molecular catalysis A: Chemical 414 (2016) 62-71.
  19. T.R. Reina, S. Ivanova, M.A. Centeno, J.A. Odriozola “The role of Au, Cu & CeO2 and their interactions for an enhanced WGS performanceApplied Catalysis B: Env. 187 (2016) 98-107.
  20. T.R. Reina, S. Ivanova, M.A. Centeno, J.A. Odriozola “WGS and CO-PrOx reactions using gold promoted copper-ceria catalysts: Bulk CuO-CeO2 vs. CuO-CeO2/Al2O3 with low mixed oxide content” Applied Catalysis B: Environmental 197 (2016) 62–72.
  21. T.R. Reina, P. Yeletski, J.M. Bermudez , P. Arcelus-Arrillaga, V. A. Yakovlev, M.Millan “Anthracene aquacracking using NiMo/SiO2 catalysts in supercritical water conditionsFuel 182 (2016) 740- 748.
  22. J.L. Santos, T.R. Reina, S. Ivanova, M.A. Centeno, J.A. Odriozola “Gold promoted Cu/ZnO/Al2O3 catalysts prepared from hydrotalcite precursors: Advanced materials for the WGS reaction” Applied Catalysis B: Environmental 201 (2017) 310–317
  23. M.A. Centeno, T.R. Reina, O.H. Laguna, S. Ivanova, J.A. Odriozola. “Au/CeO2 catalysts: structure and CO oxidation activity” Catalysts 6 (2016) 158
  24. P. Boldrin, E. Ruiz-Trejo, J. Mermelstein, J.M. Bermudez, T.R. Reina, N. Brandon "Strategies for carbon and sulfur tolerant solid oxide fuel cell materials, incorporating lessons from heterogeneous catalysis" Chemical Reviews 2016, 116 (22) 13633–13684
  25. R. Volpe, J.M. Bermúdez, T.R. Reina, A. Messineo, M. Millan “Evolution of chars during slow pyrolysis of citrus waste” Fuel Processing Technology 158 (2017) 255–263
  26. C. Price, L. Pastor-Pérez, E. le Saché, A. Sepúlveda-Escribano, T.R. Reina “Highly active Cu-ZnO catalysts for the WGS reaction at medium-high space velocities: effect of the support composition” International Journal of Hydrogen Energy 42 (16) (2017) 10747-10751.
  27. E. le Saché, Y. Peng, H. Arellano-Garcia, T.R. Reina, “Model-Based Analysis and Integration of Synthetic Methane Production and Methane Oxidative Coupling” Computer Aided Chemical Engineering 40 (2017) 1147-1152
  28. H. Arellano-Garcia, E. Ketabchi, T.R. Reina “Integration of Bio-refinery Concepts in Oil Refineries” Computer Aided Chemical Engineering 40 (2017) 829-834
  29.  T.J. Smith, E. Le Saché, H. Arellano-Garcia, T.R. Reina “Advanced Ni-CeO2 nanocatalysts for chemical CO2 recyclingAlChE 2017 Annual meeting 1 211-212
  30. T. Stroud, T.J. Smith, E. Le Saché, H. Arellano-Garcia, T.R. Reina “Improving the Performance of Sn Promoted Ni/Al2O3 Catalysts for the Dry Reforming of Methane” AlChE 2017 Annual meeting 1 215-216
  31.   H. Arellano-Garcia, E. Ketabchi, T.R. Reina Towards bio refinery process integration in oil refineries AlChE 2017 Annual meeting 1 146-149
  32. L. Pastor-Pérez, F. Baibars, E. Le Sache, H.  Arellano-García, S. Gu, T.R. Reina CO2 valorisation via Reverse Water-Gas Shift reaction using advanced Cs doped Fe-Cu/Al2O3 catalysts. Journal of CO2 utilization 21 (2017) 423-428
  33.  D. Sebastia-Saez, T.R. Reina, H. Arellano-Garcia  Numerical Modelling of Braiding and Meandering Instabilities in Gravity-Driven Liquid Rivulets Chemie Ingenieur Technik 89 (11) 1515-1522
  34.  L. Pastor-Pérez, E. Le Saché, C. Jones, S. Gu, H. Arellano-Garcia, T. R. Reina Synthetic Natural Gas production from CO2 over Ni-x/CeO2-ZrO2 (x = Fe, Co) catalysts: Influence of promoters and space velocity Catalysis Today in press.
  35. Pirou, J.M. Bermudez Menendez, P. V. Hendriksen, A.s Kaiser, T. R. Reina, M.Millan, R. Kiebach   “Stability and performances of robust dual-phase (ZrO2)0.89(Y2O3)0.01(Sc2O3)0.10- Al0.02Zn0.98O1.01 oxygen transport membranes” Journal of Membrane Science 543 (2017) 18-27
  36. V. Katranidis, S. Gu, T.R. Reina, E. Alpay, B. Allcock, S. Kamnis Experimental study of high velocity oxy-fuel sprayed WC-17Co coatings applied on complex geometries. Part B: Influence of kinematic spray parameters on microstructure, phase composition and decarburization of the coatings Surface & Coatings Technology 328 (2017) 499–512
  37. T. Stroud, T.J. Smith, E. Le Saché J.L. Santos, M.A. Centeno, H. Arellano-Garcia, J.A. Odriozola, T.R. Reina “Chemical CO2 recycling via dry and bi reforming of methane using Ni-Sn/Al2O3 and NiSn/CeO2-Al2O3 catalysts” Applied Catalysis B: Environmental 224 (2018) 125–135
  38. Pirou, J.M. Bermudez Menendez, P. V. Hendriksen, A.s Kaiser, T. R. Reina, M.Millan, R. Kiebach   “Performance and stability of (ZrO2)0.89(Y2O3)0.01(Sc2O3)0.10-LaCr0.85Cu0.10Ni0.05O3-δ oxygen transport membranes under conditions relevant for oxy-fuel combustion” Journal of Membrane Science 552 (2018) 115-123.
  39. L. Yang, L. Pastor-Pérez, S. Gu, A. Sepúlveda-Escribano, T. R. Reina “Highly efficient Ni/CeO2-Al2O3 catalysts for CO2 upgrading via Reverse Water-Gas Shift: Effect of selected transition metal promotersApplied Catalysis B: Environmental 232 (2018) 464–47
  40. E. Le Saché , L. Pastor Perez , D. Watson , A. Sepúlveda-Escribano , T.R. Reina “Ni stabilised on inorganic complex structures: superior catalysts for chemical CO2 recycling via dry reforming of methane”, Applied Catalysis B: Environmental 236 (2018) 458-465
  41. I. Unal, S. Meisuria, M. Choolaei, T.R. Reina, B. Amini Horri. 'Synthesis and Characteristics of Nanocrystalline Ni1-xCoxO/GDC Powder as a Methane Reforming Catalyst for SOFCs'. Ceramics International 44 (2018) 6851–6860
  42. J. M Bermudez, J. Garcia-Fayos, T.R. Reina, G. Reed, E. S. Persoon, D. Görtz, M.Schroeder, M. Millan, Jose M Serra “Thermochemical stability of LaxSr1-xCoyFe1-yO3-δ and NiFe2O4-Ce0.8Tb0.2O2-δ under real conditions for its application in 4-end module oxygen transport membranes for oxy-combustionJournal of Membrane Science (2018) 562 26-37.
  43. E. Le Saché, J.L. Santos, T.J. Smith, M.A. Centeno , H. Arellano-Garcia, T.R. Reina “Multicomponent Ni-CeO2 Nanocatalysts for Syngas production from CO2/CH4 mixtures” Journal of CO2 utilization  25 (2018) 68-78.
  44.   J.L. Santos, T.R. Reina, S. Ivanova, M.A. Centeno, J.A. Odriozola Multicomponent Au/Cu-ZnO-Al2O3 catalysts: Robust materials for clean hydrogen production Applied Catalysis A 558  (2018) 91-98.
  45. C.A.H. Price, L. Pastor-Perez, T.R. Reina, J. Liu, “Robust mesoporous bimetallic yolk–shell catalysts for chemical CO2 upgrading via dry reforming of methaneReact. Chem. Eng. (2018) 3 433-436. Back Cover paper
  46. U. Guharoy, Q.Cai, E. Le Saché, S. Gu, T. R. Reina Understanding the role of Ni-Sn interaction for highly efficient chemical CO2 recycling via dry reforming of methane Jounal of CO2 utlization 27 (2018) 1-10.
  47. A. Cardoso, T. R. Reina,  I. Suelves, J.L. Pinilla, M. Millan, K. Hellgardt Effect of carbon-based materials and CeO2 on Ni catalysts for Kraft lignin liquefaction in supercritical water Green Chemistry (2018)   20(18) 4308-4318
  48. P.M. Yeletsky, T.R. Reina, O.A. Bulavchenko, A.A. Saraev, E.Yu. Gerasimov, O.O. Zaikina, J.M. Bermúdez, P. Arcelus-Arrillaga, V.A. Yakovlev, M.Millan, Phenanthrene catalytic cracking in Supercritical Water: effect of the reaction conditions on NiMo/SiO2 catalysts Catalysis Today 329 (2019) 197–205
  49. F. Baena, M Rodriguez, F. Vega, T. Reina, L. Vilches, B. Navarrete Regeneration of Sodium Hydroxide from a Biogas Upgrading Unit through the Synthesis of Precipitated Calcium Carbonate: An Experimental Influence Study of Reaction Parameters Processes 6(11) 2018 205.
  50. Pastor-Pérez, S. Gu, A. Sepúlveda-Escribano, T. R. Reina Bimetallic Cu-Ni catalysts for the WGS reaction – cooperative or uncooperative effect? International Journal of Hydrogen Energy 44(8) 2019 4011-4019.
  51. E. Le Saché, L.Pastor Perez, V. Garcilaso, M.A. Centeno, J.A. Odriozola, T.R. Reina La2Zr2-xNixO7-δ pyrochlore-perovskite catalyst for H2-rich syngas production using CO2/CH4 as feedstock Cataysis Today (2019) in press 
  52. W. Jin, L.Pastor- Pérez, D. Shen,  A. Sepúlveda-Escribano,  S. Gu, T. R.Reina Catalytic upgrading of biomass model compounds: Novel approaches and lessons learnt from traditional hydrodeoxygenation – a review ChemCatChem 2019, 11, 1–38.
  53. L. Pastor Perez,M. Saha, E. Le Saché, T.R. Reina Improving Fe/Al2O3 Catalysts for the Reverse Water-Gas Shift Reaction: On the Effect of Cs as Activity/Selectivity Promoter  Catalysts 2018, 8, 608.
  54. S.Rood, .B. Ahmet, A. Gomez, L.Torrente-Murciano, T. R. Reina S. Eslava Enhanced Ceria Nanoflakes using Graphene Oxide as a Sacrificial Template for CO Oxidation and Dry Reforming of Methane Applied Catalysis B: Environmental 242 (2019) 358–368
  55. Q. Zhang,L.Pastor Perez,W. Jin, S. Gu, T.R. Reina Understanding the promoter effect of Cu and Cs over highly effective β-Mo2C catalysts for the reverse water-gas shift reaction Applied Catalysis B: Environmental 244 (2019) 889–898.
  56. X. Liu, G. Lan, P. Su, L. Qian, T. R. Reina, L. Wang,Y. Li, J. Liu Ru Higly stable Ru nanoparticles incorporated in mesoporous carbon catalysts for production of γ- valerolactone Catalysis Today in press.
  57. C.A.H. Price, E. Earles, L. Pastor-Perez, J. Liu, T.R. Reina, Advantages of Yolk Shell Catalysts for the DRM: A Comparison of Ni/ZnO@SiO2 vs Ni/CeO2 and Ni/Al2O3 Chemistry 1 (2019) 3-16.
  58. U. Guharoy, Q.Cai, E. Le Saché, S. Gu, T. R. Reina Theoretical insights of Ni2P (0001) surface towards its potential applicability in CO2 conversion via dry reforming of methane ACS catalysis  (2019) 9, 4 3487-3497
  59.  V. Patel, L. Pastor-Perez, E. Le Sache, T.R. Reina CO2 methanation in the presence of methane: catalysts design and effect of methane concentration in the reaction mixture Journal of the Energy Institute 2019 In press
  60. E. Portillo, F. Vega, M. Cano, T.R. Reina, F. Navarrete, Understanding the thermochemical behavior of La0.6Sr0.4Co0.2 Fe0.8O3 and Ce0.9 Gd0.1O_Co oxygen transport membranes under real oxy-combustion process conditions Solid State Ionics 341 (2019) 115039
  61. F. Baena, M Rodriguez, F. Vega, T. Reina, L. Vilches, B. Navarrete Understanding the Influence of the alkaline cation K+ or Na+ in the Regeneration Efficiency of a Biogas Upgrading Unit International Journal of energy Research 43 (2019) 1578–1585
  62. F. Baena, M Rodriguez, F. Vega, T.R. Reina, L. Vilches, B. Navarrete  Synergizing   carbon storage acapture  in a biogas upgrading lab-scale plant based on calcium chloride: Influence of precipitation parameters Science of the Total Environment 670 (2019) 59-66
  63. Estelle le Saché,Sarah Johnson,Laura Pastor-Pérez,Bahman Amini Horri, Tomas R. Reina Biogas Upgrading Via Dry Reforming Over a Ni-Sn/CeO2-Al2O3 Catalyst: Influence of the Biogas Source Energies 2019, 12, 1007.
  64. F. Baena, C.A. Price, Estelle le Saché, L.Pastor-Perez, D. Sabastia-Saez,T.R.  Reina Physicochemical Comparison of Precipitated Calcium Carbonate for Different Configurations of a Biogas Upgrading Unit Journal of Chemical Technology & Biotechnology  94 (2019) 2256–2262
  65. E. Le Saché, L.Pastor Perez, V. Garcilaso, M.A. Centeno, J.A. Odriozola, T.R. Reina La2Zr2-xNixO7-δ pyrochlore-perovskite catalyst for H2-rich syngas production using CO2/CH4 as feedstock Cataysis Today - article in press
  66. F. Baena, M Rodriguez, F. Vega, T.R. Reina, L. Vilches, B. Navarrete Converting CO2 from Biogas and MgCl2 Residues into Valuable Magnesium Carbonate: a Novel Strategy for Renewable Energy Production  Energy 180 (2019) 457-464
  67. E. Ketabchi, L.Pastor-Pérez, T. R. Reina, H. Arellano-Garcia Integration of Fossil Fuel-based with Bio-based Industries: The Use of Waste Streams and Biomass to Produce Syngas and Added Value Products IFAC PapersOnLine 52-1 (2019) 616-621
  68. C. Megias,   T. R. Reina,S.Ivanova, J.A. Odriozola  Au/CeO2-ZnO/Al2O3 as Versatile Catalysts for Oxidation Reactions: Application in Gas/Liquid Environmental Processes Front. Chem.,  2019 (7) 504
  69. W. Jin, J.L. Santos, L.Pastor- Pérez, S.Gu, M.A. Centeno, T. R.Reina Noble metal supported on activated carbon for "hydrogen free" HDO reactions: exploring economically advantageous routes for biomass valorisation ChemCatChem 2019,11, 4434–4441
  70. F. Baena, M Rodriguez, T.R. Reina, Z. Zhang L. Vilches, B. Navarrete  Understanding the effect of Ca and Mg ions from wastes in the solvent regeneration stage of a biogas upgrading unit Science of the Total Environment 670 (2019)  93-100.
  71. R. Volpe, J.M. Bermúdez, T.R. Reina, M.Volpe, A. Messineo, M. Millan, M Titirici "Free radicals formation on thermally decomposed biomass" Fuel 255 (2019) 115802
  72. H.Rodriguez, J.L. Santos, M.I. Dominguez, T.R. Reina, S. Ivanova, M.A. Centeno, J.A. Odriozola Carbon Supported gold nanoparticles for the catalytic reduction of 4-nitrophenol Front. Chem.,  2019 doi: 10.3389/fchem.2019.00548  
  73. W. Jin, L.Pastor- Pérez, J.J. Villora, S.Gu, A.Sepulveda-Escrinabo, T. R.Reina Investigating new routes for biomass upgrading: "H2-free" HDO using Ni-based catalysts ACS Sustainable Chemistry and Engineering (2019) 
  74. Utsab Guharoy, Tomas Ramirez Reina, Sai Gu and Qiong Cai Mechanistic Insights Into Selective CO 2 Conversion via RWGS on Transition Metal Phosphides: A DFT Study Journal of Physical Chemistry C - 2019, 123, 37, 22918-22931.
  75. C.A. Price, L. Pastor-Perez, S. Ivanova, T.R. Reina, J. Liu The Success Story of Gold-Based Catalysts for Gas- and Liquid-Phase Reactions: A Brief Perspective and Beyond Front. Chem. 2019 7:691
  76. J.Yu, J.A. Odriozola, T.R. Reina Dry Reforming of Ethanol & Glycerol: A mini-review Catalysts 2019 (9) 12 1015
  77. N. Nityashree, C. A. H. Price, L. Pastor-Perez, G. V. Manohara, S. Garcia, M. M. Maroto-Valer, T. R. Reina Carbon Stabilised Saponite Supported Transition Metal-Alloy Catalysts for Chemical CO2 Utilisation via Reverse Water-Gas Shift Reaction Applied Catalysis B: Environmental 261 (2020) 118241
  78. F. Baena, F. Vega, L.Pastor-Perez, T.R. Reina, Navarrete ,Z. Zhang, B. Novel Process for Carbon Capture and Utilization and Saline Wastes Valorization Journal of Natural Gas science and Engineering 73 (2020) 10371
  79. C.A. Price, W. Arnold, L. Pastor-Perez, B.Amini-Horri, T.R. Reina Catalytic upgrading of a biogas model mixture via low temperature DRM using multicomponent catalysts Topics in Catalysis 2020 DOI:10.1007/s11244-019-01216-8
  80. E. Ketabchi, L.Pastor-Perez, H. Arellano-Garcia, T.R. Reina  Influence of Reaction Parameters on the Catalytic Upgrading of an Acetone, Butanol and Ethanol (ABE) Mixture: Exploring New Routes for Modern Biorefineries Frontiers in Chemistry 2020 doi: 10.3389/fchem.2019.00906 
  81. S.Ivanova, J.Liu, T.R. Reina Editorial: Catalysis by Gold for Gas & Liquid Phase Reactions: A Golden Future for Environmental Catalysis Frontiers in Chemistry 2020 doi: 10.3389/fchem.2019.00891
  82. W.Jin, L.Pastor-Perez, J.J. Villora-Pico, M.M. Pastor, S.Gu, N. Charisou, A. Sepulveda-Escribano, M.A. Goula, T.R. Reina Catalytic conversion of palm oil to bio-hydrogenated diesel over novel N-doped activated carbon supported Pt nanoparticles Energies 2020, 13, 132
  83. W.Jin, L.Pastor-Perez, J.Yu, S.Gu, J.A. Odriozola, T.R. Reina Cost-effective routes for Catalytic Biomass Upgrading Current Opinion in Green and Sustainable Chemistry  23 (2020) 1-9
  84. E. Portillo, F. Vega, M. Cano, T.R. Reina, F. Navarrete, Thermochemical evaluation of oxygen transport membranes under oxy-combustion conditions in a pilot-scale facility  -Journal of Chemical Technology & Biotechnology Accepted manuscript 
  85. L.Yang, L. Pastor-Perez,J.J. Villora, S.Gu, A.Sepulveda-Escrinabo, T. R.Reina CO2 Valarosiation via Reverse Water-Gas Shift reaction using Fe/CeO2-Al2O3 catalyts: showcasing the potential of advanced catalysts to explore new processes design Applied Catalysis A: Gen.   593 (2020) 117442
  86. T. BullM. Choolaei, T.R. Reina, B. Amini Horri , Synthesis and characterisation of nanocrystalline CuO-Fe2O3/GDC anode powders for solid oxide fuel cells - Ceramics International (2020)
  87. E. le Sache, B.J. Haycock, L.Pastor-Perez, JJ. Villora-Pico,A. Sepulveda-Escribano, T.R. Reina,  Switchable  for chemical CO2 recycling: A step forward on the methanation and reverse water gas shift reactions ACS Sustainable Chemistry and Engineering  (2020)  8(11) 4614
  88. D. Sebastia-Saez, T.R.Reina, R. Silva, H. Arellano-Garcia Synthesis, characterisation and simulation of charge/discharge cycles of n-octacosane@silica phase-change nano-capsules International Journal of Energy Research 2020 (44) 2306

  89. F. Baena, L.Pastor-Perez,Q. Wang, T.R. Reina Bio-methane and bio-methanol co-production from biogas: A profitability analysis to explore new sustainable chemical processes Journal of Cleaner Production (2020) 265,121909 

  90. E. Ketabchi, L.Pastor-Perez, H. Arellano-Garcia, T.R. Reina Catalytic upgrading of acetone, butanol and ethanol (ABE): A step ahead for the production of added value chemicals in bio-refineries Renewable Energy 156 (2020) 1065-1075 

  91. J. Li, Q.Zhang, J.Liu,  M. Yu, J.Yang,  S. Ye, T. R. Reina, J. liu In-situ formation of carboxylate species on TiO2 nanosheets for enhanced visible-light photocatalytic performance Journal of Colloid & Interface Science  Accepted manuscript 

  92. F. Baena, L.Pastor-Perez,Z. Zhang, T.R. Reina  Steeping towards a low-carbon economy. Formic Acid from biogas as case of study Applied Energy 268 (2020) 115033  

  93. F. Baena, D.Sebastia ,Q. Wang, T.R. Reina Is the production of biofuels and bio-chemicals always profitable? Co-production of biomethane and urea from biogas as case study Energy Conversion and Management Accepted (2020) 220,113058

  94. Naveed Altaf, Shuyu Liang, Rashid Iqbal, Mazhar Hayat, Tomas Ramirez Reina, Qiang Wang Cu-CuOx/rGO catalyst derived from LDH/GO hybrid with enhanced C2H4 selectivity by CO2 electrochemical reduction Journal of CO2 utilization Accepted manuscript

  95. F. Baena, E.Le Sache ,L.Pastor-Perez, T.R. Reina Membranes-based technologies for biogas upgrading Environmetal Chemistry Letters (2020) in press

  96. Qi Zhang, Laura Pastor-Pérez, Sai Gu, Tomas Ramirez Reina Transition Metal Carbides (TMCs) catalysts for gas phase CO2 upgrading reactions: a comprehensive overview  Catalysts 2020, 10(9), 955 

  97. F. Baena, Z.Zhang, X. Zhang, T.R. Reina Profitability analysis of a novel configuration to synergize Biogas Upgrading and Power-to-Gas Energy Conversion and Management (2020) Accepted manuscript

  98. Z. Wang, L. Huang, T. R. Reina, A.M,Efstathious, Q. Wang Aqueous Miscible Organic LDH Derived Ni-Based Catalysts for Efficient CO2 Methanation Catalysts  2020, 10, 1168.

  99. Alejandro Pérez-Flórez, Katherine Archila, Ana-María Campos, Lorena Lugo, Crispin Celis, Sonia Moreno, Tomas Ramirez Reina Influence of the active phase (Fe, Ni and Ni-Fe) of mixed oxides in CWAO of Crystal Violet Catalysts (2020) Accepted draft

  100. A.B. Dongil, Q. Zhang, L.Pastor-Perez, T.R. Reina, A. Guerrero, I. Rodriguez-Ramos Effect of Cu and Cs in the B-Mo2C System for CO2 Hydrogenation to Methanol Catalysts 2020, 10, 1213

  101. C.A. Price, T.R. Reina, J. Liu Engineering Heterogenous Catalysts for Chemical CO2 Utilization: Lessons from Thermal Catalysis and Advantages of Yolk@Shell Structured Nanoreactors Journal of Energy Chemistry 2021, 57, 304-324 

  102. L. Pastor-Perez, W.Jin, J.J. Villora-Pico, Q. Wang, A. Sepulveda-Escribano, T.R. Reina  "H2-free" demethoxylation of guaiacol in subcritical water using Pt supported on N-doped carbon catalysts: A cost-effective strategy for biomass upgrading Journal of Energy Chemistry 2021, 58, 377-385.

  103. F. Baena, L. Vilches, T.R. Reina, B. Navarrete  Synergizing carbon capture and utilization in a biogas upgrading plant based on calcium chloride: Scaling-up and profitability analysis Science of the Total Environment, 2021, 758, 143645 

  104. S. Parrilla-Lahoz, W. Jin, L. Pastor-Pérez, A.B. Dongil, T.R. Reina  Guaiacol hydrodeoxygenation in hydrothermal conditions using N-doped reduced graphene oxide (RGO) supported Pt and Ni catalysts: Seeking for economically viable biomass upgrading alternatives Applied Catalysis A (2021) 611, 117977 

  105. Run-Ping Ye, Lin Liao Tomas Ramirez Reina, Jiaxu Liu,  Durgaiah Chevella,  Yonggang Jin,  Maohong Fan,  Jian Liu Engineering Ni/SiO2 Catalysts for Enhanced CO2Methanation Fuel, 2021, 285, 119151

 

Edited Books

1. T.R. Reina & Jose A. Odriozola Heterogeneous Catalysis for Energy Applications - Royal Society of Chemistry ISBN: 978-1-78801-718-3

2. T.R.Reina, H.Arellano-Garcia, J.A. Odriozola Engineering Solutions for CO2 Conversion - Wiley & Sons ISBN:9783527346394

Chapters in books

1. T.R. Reina, Miriam González Castaño, Sandra Palma del Valle, Svetlana Ivanova, José Antonio Odriozola "20 years of golden future in WGS reaction" in Heterogenous gold catalysts and catalysis. RSC catalysis book series. Eds. Z.Ma and S.Da. Chapter 5. ISBN: 978-1-84973-917-7.

2. T.R. Reina, J.L Santos, N. García-Moncada, S. Ivanova and J.A. Odriozola “Development of robust mixed-conducting membranes with high permeability and stability” in Perovskites and Related Mixed Oxides Eds. Pascal Granger: Pascal Granger, Vasile Parvulescu, Serge Kaliaguine and Wilfrid Prellier Wiley-VCH, Weinheim. Chapter 32. ISBN 978-3-527-33763-7

3. L. Pastor-Perez, T.R. Reina, S. Ivanova, M.A. Centeno, A. Sepulveda, J.A. Odriozola “Ni/CeO2/C catalysts with enhanced OSC for the WGS reaction” Feature Papers to Celebrate the Landmarks of Catalysts Ed. K. Hohn ISBN 978-3-03842-221-1.

4. L. Pastor-Perez, E. le Sache,  T.R. Reina "Gas phase reactions for chemical CO2 upgrading" in Carbon Dioxide Utilisation North, Styring (Ed.) 2019 ISBN 978-1-11-066503-1

5. F. M. Baena-Moreno, E. le Saché, L. Pastor-Pérez, T. R. Reina “Biogas as a Renewable Energy Source. Focusing on Principles and Recent Advances of Membrane-Based Technologies for Biogas Upgrading” in Membranes for Environmental Applications. Environmental Chemistry for a Sustainable World 42. Chapter 3, Springer. Eds Z. Zhang, W. Zhang and E. Lichtfhouse. ISBN 978-3-030-33977-7

Patents

1. J.A. Odriozola, T.R. Reina, M. A. Centeno, S. Ivanova, V. Idakiev, T. Tabakova, "Gold catalysts and the use thereof in the water-gas shift reaction " PCT/ES2012/070717 – WO2013057347

2. J.A. Odriozola, T.R. Reina, J. L. Santos, M.A. Centeno, S. Ivanova, V.Idakiev, T. Tabakova “Gold catalysts supported on CuO/ZnO/Al2O3, production method and use thereof” PCT/ES2015/000138 – WO2016059268

3. M. Millan, T.R. Reina, J. M. Bermudez, J. L. Pinilla, H. Puron “Catalysts for processing heavy oils and its preparation method” PCT/RU2015/000546 – WO2017018505

4. T.R Reina, E. Le Sache, L. Pastor-Perez, D. Watson, A. Sepulveda, S. Gu “Catalysts for the reforming of gaseous mixtures” PCT/GB2018/050621

5. E. Ketabchi, L.Pastor-Perez, H. Arellano-Garcia, T.R. Reina " Efficient Catalyst and Processes for ABE upgrading" Application number GB1902718.4

News

In the media

Cost-effective ‘supercatalyst’ recycles CO2 and CH4 
IChemE - The Chemical Engineer
Dec 2017
Researchers Refine Reforming Catalysts
https://www.chemicalprocessing.com/articles/2017/researchers-refine-reforming-catalysts/
Chemical Processing

My publications

Publications

le Saché Estelle, Tsaousis Panayiotis, Reina Tomas Ramirez, Ruiz-Trejo Enrique (2020)High Channel Density Ceramic Microchannel Reactor for Syngas Production, In: Energies (Basel)13(23) MDPI AG
Solid oxide fuel cells can operate with carbonaceous fuels, such as syngas, biogas, and methane, using either internal or external reforming, and they represent a more efficient alternative to internal combustion engines. In this work, we explore, for the first time, an alumina membrane containing straight, highly packed (461,289 cpsi), parallel channels of a few micrometers (21 mm) in diameter as a microreformer. As a model reaction to test the performance of this membrane, the dry reforming of methane was carried out using nickel metal and a composite nickel/ceria as catalysts. The samples with intact microchannels were more resistant to carbon deposition than those with a powdered sample, highlighting the deactivation mitigation effect of the microchannel structure. The coke content in the microchannel membrane was one order of magnitude lower than in the powder catalyst. Overall, this work is a proof of concept on the use of composite alumina membrane as microchannel reactors for high temperature reactions.
It has become increasingly important to control carbon dioxide (CO¬2) emissions and at the same time generate fuel sources to meet the growing global energy consumption need. CO2 (dry) reforming of methane (DRM) is a viable process as it generates fuel (syngas) and utilises greenhouse (CH4 and CO2) gas at the same time. The success of this process relies on the development of suitable noble-metal free catalysts. First principle’s based computational methods, such as density functional theory (DFT), has become a powerful predictive tool for catalyst development in modern science. Therefore the main objective of this thesis work has been to investigate suitable catalysts using computational methods for gas–phase CO2 utilisation reactions. In this research work, DFT calculations provided us with the fundamental insights into the DRM mechanism over bimetallic Sn/ Ni (111) periodic model surfaces. This analysis showed that low Sn concentration on Ni surface effectively mitigates carbon formation without compromising the CO2 conversion and the syngas production, showcasing superior characteristics of the bimetallic catalyst towards carbon tolerance stability. Other heterogeneous catalysts such as Ni2P and MoP have also been studied in this thesis. Theoretical analysis of DRM reaction on the unexplored nickel phosphide Ni2P (0001) surface showcased suitable syngas production under DRM reaction temperatures with low carbon deposition formation on the surface. This was mainly attributed to a lower number of active sites available for carbon adsorption compared to oxygen on the Ni2P (0001) surface. DFT study on activation of CO2 and CO on MoP (0001) and Ni2P (0001) surfaces showcased selective CO production from CO2 to be possible on both the surfaces. Further, direct CO activation is favoured on the MoP (0001) surface. Surface bounded oxygen removal on Ni2P (0001) is reasonably favourable. Findings from this thesis work will be beneficial in developing more robust catalysts for gas phase CO2 utilisation reactions and could contribute to a better understanding of CO2 conversion processes, catalysts deactivation and thus helping to develop new families of powerful catalysts for a greener society
CO2 utilisation is becoming an appealing topic in catalysis science due to the urgent need to deal with greenhouse gases (GHG) emissions. Herein, the dry reforming of methane (DRM) represents a viable route to convert CO2 and CH4 (two of the major GHG) into syngas, a highly valuable intermediate in chemical synthesis. Nickel-based catalysts are economically viable materials for this reaction, however they show inevitable signs of deactivation mainly caused by the agglomeration of the active phase and carbon deposition on the surface of the catalyst. In this work, stabilisation of Ni in a pyrochlore-perovskite structure is reported as a viable method to prevent fast deactivation. Substitution of Zirconium by Ni at various loadings in the lanthanum zirconate pyrochlore La2Zr2O7 is investigated in terms of reactant conversions under various reaction conditions. Crystallographic analysis of the catalysts showed the formation of phases corresponding to the pyrochlore structure La2Zr2-xNixO7-δ and an additional La2NiZrO6 perovskite phase at high Ni loadings. The pyrochlore mixed oxide shows high basicity and surface oxygen availability, leading to a material with high CO2 activation potential. In particular, the formation of lanthanum oxycarbonate is occurring upon CO2 activation. The best formulated catalyst shows excellent activity for various reforming reactions at temperatures as low as 600 °C and displays great stability over 350 hours of continuous dry operation. Versatility in feed ratio and syngas production was demonstrated. Carbon formation although inevitable, is limited using this formulation strategy. The presence of nanosized Ni particles contributes to the excellent performance of the catalyst. Exsolution of Ni from the host lattice is believed to occur upon activation pre-treatment of the catalyst and leads to small, well dispersed and highly active Ni clusters. Overall, this work showcases an appealing strategy to design economically viable advanced catalysts for chemical CO2 recycling via reforming reactions.
Crystallisation by precipitation is a very common technique in industry, however the crystals produced are often of poor quality, characterised by broad particle size distribution and morphological inhomogeneities. These problems can be overcome by the use of ultrasound. Sonocrystallisation, or ultrasound-assisted crystallisation, has already demonstrated its general benefits in terms of reduction in crystallisation time, smaller and more homogeneous crystals and repeatability. However, there are many issues still unaddressed, such as poor knowledge of the mechanism of sonocrystallisation and of the governing parameters of the whole system. This is largely attributed to lack of systematic studies, varying frequency and power while using the same equipment, as well as difficulties in comparing results from different systems. Furthermore, ultrasound is still considered uneconomical in industrial scale, due to its high energy demand. Therefore, there is the necessity of optimising the use of ultrasound for guaranteeing a high-quality product with the lowest energy consumption. This thesis therefore focused on studying the effects of sonocrystallisation for two different crystallisation systems by precipitation: the antisolvent crystallisation of sodium chloride and the reactive crystallisation of ZIF-8, a type of Metal-Organic Frameworks (MOFs). In both systems, frequency, power and sonication time was systematically varied, and the effects on the product obtained investigated. The effect of changing supersaturation was also studied. The comparison between a simpler and a more complex system could help on obtaining general conclusions useful for clarifying the mechanism of sonocrystallisation. The antisolvent sonocrystallisation of sodium chloride revealed that sonication caused a reduction of the crystal size up to 10 times with respect to unsonicated conditions. This was achieved within a few seconds of sonication (5 s for high supersaturation and 15 s for low supersaturation), indicating that the effects of ultrasound were on the nucleation, causing the rapid formation of small and regular crystals. Phenomena of sono-fracture was excluded because the crystals formed were morphologically regular, very different from fragments. Adding a subsequent step in silent conditions or using intermittent ultrasound bursts coupled with silent conditions showed a limited crystal growth. Hence, ultrasound uses the majority of the solute forming new small crystals and leaving in the solution only a small amount of sodium chloride. The effects of different frequencies and powers were more evident at lower supersaturations, with lower frequency being more effective at reducing crystal size. However, under these conditions, although a small average crystal size was obtained, the particle size distributions were bimodal at low power. At high supersaturation, this bimodality disappeared even at low powers. For the reactive crystallisation of ZIF-8 at high excess of ligand, it was confirmed that the action of ultrasound caused a reduction of the crystal size up to nanometre. Furthermore, it was demonstrated again that the action of sonication was on the early stages of the crystallisation. However, the effects of ultrasound resembled a lot the results obtained when only mixing was applied, suggesting that sonication was not directly influencing the chemistry of the reaction. In addition, the BET surface area appeared to be related to the power used, reaching a maximum and decreasing beyond a certain power. This suggests that a competition between micromixing, causing an increase of the BET surface area, and shockwaves, responsible of breaking the framework during its formation. On the other hand, when a low excess of ligand was used, it was revealed that the formation of by-products was accelerated when mixing or sonication were applied. However, if shorter reaction time was applied, it was possible to obtain a reasonable quality of ZIF-8 at low excess of ligand. This new insight explains why low excess of ligand was considered unsuitable for ZIF-8 production, as all reported studies in the literature have applied mixing and used long reaction times. Overall, the results from this thesis have demonstrated commonalities between antisolvent and reactive crystallisation, that is reducing the sonication time to a brief interval at the beginning of the crystallisation can achieve the same size reduction as sonicating for the entire process. This is a key result in view of optimising sonocrystallisation processes. In addition, lower supersaturations or excess ligands are more sensitive to the crystallisation condition. The effect of frequency and power is more significant under antisolvent crystallisation, whereas under reactive crystallisation mixing is the dominant effect and therefore no frequency or power effect is observed. These differences may explain why there are inconsistencies in the reported frequency and power effects in the literature.
Liu Jian, Price Cameron Alexander Hurd, Pastor-Perez Laura, Ramirez Reina Tomas Yolk-Shell structured NiCo@SiO₂ nanoreactor for CO₂ upgrading via reverse water-gas shift reaction, In: Catalysis Today Elsevier
This work reports the successful and simplistic synthesis of highly uniform NiCo@SiO₂ yolk@shell catalysts, with their effectiveness towards CO₂ recycling investigated within the RWGS reaction. The engineered microstructure catalysts display high CO₂ conversion levels and a remarkable selectivity for CO as main reaction product across the whole examined temperatures. Interestingly, the selectivity is affected by Ni loading reflecting a close correlation catalytic performance/material structure-composition. Further to this behaviour, the designed nanoreactor exhibits considerable deactivation resistance and performance under reaction cycling conditions and appears to demonstrate the production of larger organic molecules after qualitative analysis of the product gas by mass spectrometry. These results demonstrate the effectiveness of the spatial confinement effect, imbued to the material from its advanced morphology, through its influence of deactivation resistance and control of reactive selectivity.
Katranidis Vasileios, Gu Sai, Ramirez Reina Tomas, Alpay Esat, Allcock Bryan, Kamnis Spyros (2017)Experimental study of high velocity oxy-fuel sprayed WC-17Co coatings applied on complex geometries. Part B: Influence of kinematic spray parameters on microstructure, phase composition and decarburization of the coatings, In: Surface & Coatings Technology328pp. 499-512 Elsevier
The aim of this study is to evaluate comprehensively the effect of spray angle, spray distance and gun traverse speed on the microstructure and phase composition of HVOF sprayed WC-17 coatings. An experimental setup that enables the isolation of each one of the kinematic parameters and the systemic study of their interplay is employed. A mechanism of particle partition and WC-cluster rebounding at short distances and oblique spray angles is proposed. It is revealed that small angle inclinations benefit notably the WC distribution in the coatings sprayed at long stand-off distances. Gun traverse speed, affects the oxygen content in the coating via cumulative superficial oxide scales formed on the as-sprayed coating surface during deposition. Metallic W continuous rims are seen to engulf small splats, suggesting crystallization that occurred in-flight.
Le Saché E., Pastor-Pérez L., Garcilaso V., Watson D.J., Centeno M.A., Odriozola J.A., Reina T.R. Flexible syngas production using a La2Zr2O7-δ pyrochlore-double perovskite catalyst: Towards a direct route for gas phase CO2 recycling, In: Catalysis Today Elsevier
The bi-reforming of methane (BRM) has the advantage of utilising greenhouse gases and producing H2 rich syngas. In this work Ni stabilised in a pyrochlore-double perovskite structure is reported as a viable catalyst for both Dry Reforming of Methane (DRM) and BRM. A 10 wt.% Ni-doped La2Zr2O7 pyrochlore catalyst was synthesised, characterised and tested under both reaction conditions and its performance was compared to a supported Ni/La2Zr2O7. In particular the effect of steam addition is investigated revealing that steam increases the H2 content in the syngas but limits reactants conversions. The effect of temperature, space velocity and time on stream was studied under BRM conditions and brought out the performance of the material in terms of activity and stability. No deactivation was observed, in fact the addition of steam helped to mitigate carbon deposition. Small and well dispersed Ni clusters, possibly resulting from the progressive exsolution of Ni from the mixed oxide structure could explain the enhanced performance of the catalyst.
Choolaei Mohammadmehdi, Ramirez Reina Tomas, Amini Horri Bahman Synthesis and characterisation of nanocrystalline CuO–Fe2O3/GDC anode powders for solid oxide fuel cells, In: Ceramics International Elsevier
This paper deals with the development and potential application of a novel mixed ionic-electronic conductive anode composite comprised of copper and iron oxide based on gadolinium-doped ceria (CuO–Fe2O3/GDC) for solid-oxide fuel cell (SOFC). Synthesis of the nanocrystalline CuO–Fe2O3/GDC powders was carried out using a novel co-precipitation method based on ammonium tartrate as the precipitant in a mixed-cationic solution composed of Cu2+, Fe3+, Gd3+, and Ce3+. Thermal decomposition of the resultant precipitate after drying (at 55 °C) was investigated in a wide range of temperature (25–900 °C) using simultaneous DSC/TGA technique in air. The DSC/TGA results suggested the optimal calcination temperature of 500 °C for obtaining the nanocrystalline anode composite from the resultant precipitate. The synthesised CuO–Fe2O3/GDC samples were further characterised using XRD, dilatometry, FESEM, and EDX. Several single cells of SOFCs were fabricated in the anode-supported geometry using the synthesised CuO–Fe2O3/GDC composite as the anode, GDC/CuO composite as the electrolyte, and LSCF/GDC composite as the cathode layer. The fabricated cells were analysed using FESEM imaging and EIS analysis, where an equivalent circuit containing five R-CPE terms was used to interpret the EIS data. The module fitted well the impedance data and allowed for a detailed deconvolution of the total impedance spectra. The catalytic activity and uniformity of the synthesised nanocomposites was further evaluated using TPR analysis, demonstrating excellent activity at temperatures as low as 200 °C.
Ramirez Reina Tomas, Price Cameron Alexander Hurd, Arnold William, Pastor-Perez Laura, Amini-Horri Bahman Catalytic upgrading of a biogas model mixture via low temperature DRM using multicomponent catalysts, In: Topics in Catalysis Springer Verlag
The catalytic performance of a series of bimetallic Ni-Co/CeO2-Al2O3 catalysts were evaluated within the dry reforming of methane (DRM) reaction, commonly used for upgrading biogas. The study focused on the variation of CeO2 weight loadings between 0, 10, 20 and 30%. It was found that the addition of CeO2 promoted CH4 and CO2 conversion across the temperature range and increased H2/CO ratio for the “low temperature” DRM. X-Ray Diffraction (XRD), H2-Temperature Programmed Reduction (H2-TPR) and X-Ray Photoelectron Spectroscopy (XPS) analysis revealed the formation of Ce4+ during activation of the 30% sample, resulted in excessive carbon deposition during reaction. The lowest CeO2 weight loadings exhibited softer carbon formation and limited increased chemical stability during reaction at the expense of activity. Of the tested weight loadings, 20 wt% CeO2 exhibited the best balance of catalytic activity, chemical stability and deactivation resistance in the DRM reaction. Hence this catalyst can be considered a promising system for syngas production from biogas at relatively low temperatures evidencing the pivotal role of catalysts design to develop economically viable processes for bioresources valorisation.
Bermudez J, Garcia-Fayos J, Ramirez Reina Tomas, Reed G, Persoon E, Görtz D, Schroeder M, Millan M, Serra J (2018)Thermochemical stability of LaxSr1-xCoyFe1-yO3-δ and NiFe2O4-Ce0.8Tb0.2O2-δ under real conditions for its application in oxygen transport membranes for oxyfuel combustion, In: Journal of Membrane Science562pp. 26-37 Elsevier
This work addresses the thermochemical stability of ceramic materials –typically used in oxygen transport membranes– under the harsh gas environments found in oxyfuel combustion processes. Specifically, a dual-phase NiFe2O4-Ce0.8Tb0.2O2-δ (NFO-CTO) composite and a single-phase La0.6Sr0.4Co0.2Fe0.8O3-δ (LSCF) were studied. The effect of the main contaminants present in this kind of processes (CO2, SO2 and H2O) has been tested. NFO-CTO composite remains stable under all the conditions studied whereas LSCF presents a poor stability in the presence of CO2 and SO2. Regardless of the treatment, NFO-CTO conserves its crystalline structure, without giving rise to new species due to segregation or incorporation of sulphur and/or carbon. On the contrary, LSCF is prone to degradation in contact with CO2 and SO2, segregating Sr in the form of SrCO3 and SrSO4 and Co and Fe in the form of CoO and Fe3O4. It is also shown that SO2 interaction with LSCF is stronger than in the case of CO2. A concentration of just 2000 ppm of SO2 in CO2 is enough to subdue the formation of SrCO3, promoting the segregation of Sr only in the form of SrSO4. With the results presented in this work, it is possible to conclude that the NFO-CTO is a suitable candidate from the thermochemical viewpoint to be used as membrane material in 4-end modules for oxygen generation integrated into oxyfuel combustion processes whereas the use of LSCF should be dismissed.
Ramirez Reina T, Ivanova S, Laguna OH, Centeno MA, Odriozola JA (2016)WGS and CO-PrOx reactions using gold promoted copper-ceria catalysts: “Bulk CuO CeO2 vs. CuO CeO2/Al2O3 with low mixed oxide content”, In: Applied Catalysis B: Environmental1697pp. 62-7
A copper-ceria bulk catalyst has been compared to a series of catalysts designed according to the as called “supported approach”, corresponding to the dispersion of low content mixed copper-ceria oxide on alumina matrix. The principal characteristics of both types of catalysts are contemplated and the differences in their electronic and redox properties discussed in details. As a plus, the gold metal promotion of the catalysts is also envisaged. The advantages of the systems in the CO clean up reactions, WGS and CO-PrOx are commented. While the WGS activity appears to be ruled especially by the Cu/Ce surface to volume ratio, the CO-PrOx reaction is governed by the CuO loading. Gold addition provides benefits only at the low temperature WGS regime. Very importantly, the supported systems are always superior to the bulk configuration in terms of specific activity, a key factor from the catalyst’s design perspective.
Jin Wei, Santos Jose Luis, Pastor-Perez Laura, Gu Sai, Centeno Miguel Angel, Reina Tomas Ramirez Noble metal supported on activated carbon for "hydrogen free" HDO reactions: exploring economically advantageous routes for biomass valorisation, In: ChemCatChem Wiley
An innovative route for bio‐compounds upgrading via “hydrogen‐free” hydrodeoxygenation (HDO) is proposed and evaluated using guaiacol as a model compound in a high‐pressure batch reactor. Experimental results showed that noble metal supported on activated carbon catalysts are able to conduct tandem multiple steps including water splitting and subsequent HDO. The activity of Ru/C catalyst is superior to other studied catalysts (i.e. Au/C, Pd/C and Rh/C) in our water‐only HDO reaction system. The greater dispersion and smaller metal particle size confirmed by the TEM micrographs accounts for the better performance of Ru/C. This material also presents excellent levels of stability as demonstrated in multiple reciclabylity runs. Overall, the proposed novel approach confirmed the viability of oxygenated bio‐compounds upgrading in a water‐only reaction system suppressing the need of external H2 supply and can be rendered as a fundamental finding for the economical biomass valorisation to produce added value bio‐fuels.
Stroud T., Smith Tristan, Le Saché Estelle, Santos J.L., Centeno M.A., Arellano-Garcia Harvey, Odriozola J.A., Ramirez Reina Tomas (2017)Chemical CO2 recycling via dry and bi reforming of methane using Ni-Sn/Al2O3 and Ni-Sn/CeO2-Al2O3 catalysts, In: Applied Catalysis B: Environmental224pp. 125-135 Elsevier
Carbon formation and sintering remain the main culprits regarding catalyst deactivation in the dry and bi-reforming of methane reactions (DRM and BRM, respectively). Nickel based catalysts (10 wt.%) supported on alumina (Al2O3) have shown no exception in this study, but can be improved by the addition of tin and ceria. The effect of two different Sn loadings on this base have been examined for the DRM reaction over 20 h, before selecting the most appropriate Sn/Ni ratio and promoting the alumina base with 20 wt.% of CeO2. This catalyst then underwent activity measurements over a range of temperatures and space velocities, before undergoing experimentation in BRM. It not only showed good levels of conversions for DRM, but exhibited stable conversions towards BRM, reaching an equilibrium H2/CO product ratio in the process. In fact, this work reveals how multicomponent Ni catalysts can be effectively utilised to produce flexible syngas streams from CO2/CH4 mixtures as an efficient route for CO2 utilisation.
Megías-Sayago Cristina, Reina Tomas Ramirez, Ivanova Svetlana, Odriozola Jose A. (2019)Au/CeO2-ZnO/Al2O3 as Versatile Catalysts for Oxidation Reactions: Application in Gas/Liquid Environmental Processes, In: Frontiers in Chemistry7504pp. 1-10 Frontiers Media
The present work showcases the versatility of nanogold systems supported on Zn-doped ceria when applied in two important environmental processes, the total CO oxidation, and the liquid phase oxidation of glucose to gluconic acid. In the CO oxidation the suitability of these materials is clearly demonstrated achieving full conversions even at sub-ambient conditions. Regarding the glucose oxidation our materials display high conversion values (always over 50%) and very importantly full or almost full selectivity toward gluconic acid—an added value platform chemical in the context of biomass upgrading routes. The key factors controlling the successful performance on both reactions are carefully discussed and compared to previous studies in literature. To our knowledge this is one of the very few works in catalysis by gold combining liquid and gas phase reactions and represents a step forward in the flexible behavior of nano gold catalysts.
O transport membranes (OTM) are a promising alternative to conventional systems of air separation based on cryogenic distillation for oxy-fuel combustion power plants. In this work, a systematic study of the thermochemical stability of La0.6Sr0.4Co0.2 Fe0.8O3 (perovskite-type) and cobalt doped Ce0.9Gd0.1O (fluorite-type) is proposed. The experiments were developed in a laboratory scale facility, which is able to mimic realistic oxy-fuel combustion flue gas containing SOx, NOx, H2O and CO2. In order to understand the thermochemical behavior of this type of materials, a full characterization analysis of the tested samples using a wide portfolio of analytical techniques such as X-ray diffraction (XRD), X-ray fluorescence (XRF), infrared spectroscopy (ATR-FTIR), Raman spectroscopy, scanning electron microscopy with energy-dispersive X-ray spectroscopy (SEM-EDS) and Brunauer−Emmett−Teller analysis (BET) has been carefully discussed. Our data revealed the superior stability of the CGO samples in comparison with the LSCF at all the test conditions studied in this work. The formation of crystalline and amorphous sulphates and carbonates are evident for the LSCF while for the CGO samples do not react with SOX and barely form carbonates. The presence of silicon species – typically ignored in academic works – has been detected, pointing its relevance for real applications.
Ramirez Reina T, Yeletsky P, Bermudez JM, Arcelus-Arrillaga P, Yakovlev V, Millan M (2016)Anthracene aquacracking using NiMo/SiO2 catalysts in supercritical water conditions, In: Fuel: the science and technology of fuel and energy182pp. 740-748
A series of effective NiMo/SiO2 catalysts for heavy oil upgrading in supercritical water have been developed. Experimental results with anthracene as model compound resembling structures present in heavy oils showed that the catalytic activity as well as the liquid and gas product distributions are governed by catalyst composition. In particular by adjusting the Ni/Mo ratio different physicochemical properties (crystalline phase composition, particle size and catalysts reducibility) are obtained, which have influence on catalytic behavior. A variety of liquid products together with a valuable gas (rich in H2) are produced in this process, which takes place with remarkably low coke deposition on the catalysts. Overall, the results derived from this work confirm the viability of upgrading polyaromatic structures in supercritical water using Ni-Mo catalysts and provides an insight on the main parameters to control in catalyst design.
Odriozola JA, Ramirez Reina T, Gonzalez-Castano M, Ivanova S, Centeno MA (2014)Unrevealing the mechanism of the WGS reaction over Au/CeO2-FeOx/Al2O3 catalysts, In: Proceddings of 2014 AIChE Annual Meeting1pp. 498-499
Hydrogen-alimented fuel cells (FC) have a strong potential to play a decisive role in the new energy system for the coming years. The production of H2 pure enough to use it in fuel cells requires the development of very efficient catalysts for the WGS reaction. In our group several gold-ceria based catalysts have been developed presenting very promising results in this process [1,2]. The successful catalytic design makes mandatory an accurate knowledge about the reaction mechanism and the active species involved in the process. In order to address these issues a combination of several in-situ/operando characterization techniques is performed in this work using an optimized Au/CeO2-FeOx/Al2O3 catalyst. Synchrotron-based in-situ time-resolved Xray absorption spectroscopy (TR-XAS) and operando DRIFTS during the WGS reaction are employed with the ultimate goal to establish structure-activity relations and to propose the most likely reaction pathways.
Pirou S, Bermudez J, Tak Na B, Yu J, Vang Hendriksen P, Kaiser A, Ramirez Reina Tomas, Millan M, Kiebach R (2018)Performance and stability of (ZrO2)0.89(Y2O3)0.01(Sc2O3)0.10-LaCr0.85Cu0.10Ni0.05O3-δ oxygen transport membranes under conditions relevant for oxy-fuel combustion, In: Journal of Membrane Science552pp. 115-123 Elsevier
Self-standing, planar dual-phase oxygen transport membranes consisting of 70 vol.% (ZrO2)0.89(Y2O3)0.01(Sc2O3)0.10 (10Sc1YSZ) and 30 vol.% LaCr0.85Cu0.10Ni0.05O3-δ (LCCN) were successfully developed and tested. The stability of the composite membrane was studied in simulated oxy-fuel power plant flue-gas conditions (CO2, SO2, H2O). The analyses of the exposed composites by X-ray diffraction (XRD), X-ray fluorescence (XRF), attenuated total reflection Fourier transform infrared spectroscopy (ATR-FTIR) and Raman spectroscopy revealed an excellent stability. Oxygen permeation fluxes were measured across 1000 µm thick and 110 µm thick self-supported 10Sc1YSZ-LCCN (70-30 vol.%) membranes from 700 °C to 950 °C using air as the feed gas and N2 or CO2 as the sweep gas. The 110 µm thick membrane, prepared by tape-casting and lamination processes, showed oxygen fluxes up to 1.02 mLN cm-2 min-1 (950 °C, air/N2). Both membranes demonstrated stable performances over long-term stability tests (250-300 h) performed at 850 °C using pure CO2 as the sweep gas.
Guharoy Utsab, Ramirez Reina Tomas, Gu Sai, Cai Qiong (2019)Mechanistic Insights into Selective CO2 Conversion via RWGS on Transition Metal Phosphides: A DFT Study, In: Journal of Physical Chemistry C123(37)pp. 22918-22931 American Chemical Society
Selective conversion of CO2 to CO via the reverse water gas shift (RWGS) reaction is an attractive CO2 conversion process, which may be integrated with many industrial catalytic processes such as Fischer−Tropsch synthesis to generate added value products. The development of active and cost friendly catalysts is of paramount importance. Among the available catalyst materials, transition metal phosphides (TMPs) such as MoP and Ni2P have remained unexplored in the context of the RWGS reaction. In the present work, we have employed density functional theory (DFT) to first investigate the stability and geometries of selected RWGS intermediates on the MoP (0001) surface, in comparison to the Ni2P (0001) surface. Higher adsorption energies and Bader charges are observed on MoP (0001), indicating better stability of intermediates on the MoP (0001) surface. Furthermore, mechanistic investigation using potential energy surface (PES) profiles showcased that both MoP and Ni2P were active toward RWGS reaction with the direct path (CO2* → CO* + O*) favorable on MoP (0001), whereas the COOH-mediated path (CO2* + H* → COOH*) favors Ni2P (0001) for product (CO and H2O) gas generation. Additionally, PES profiles of initial steps to CO activation revealed that direct CO decomposition to C* and O* is favored only on MoP (0001), while H-assisted CO activation is more favorable on Ni2P (0001) but could also occur on MoP (0001). Furthermore, our DFT calculations also ascertained the possibility of methane formation on Ni2P (0001) during the RWGS process, while MoP (0001) remained more selective toward CO generation.
Archila Katherine, Campos Ana María, Lugo Lorena, Celis Crispín Astolfo, Moreno Sonia, Reina Tomas Ramirez, Pérez-Flórez Alejandro (2020)Influence of the Active Phase (Fe, Ni, and Ni–Fe) of Mixed Oxides in CWAO of Crystal Violet, In: Catalysts10(9) MDPI
The catalytic oxidation of aqueous crystal violet (CV) solutions was investigated using Ni and Fe catalysts supported over Mg–Al oxides synthesized by the autocombustion method. The influence of temperature, loading, and selectivity were studied in the catalytic wet air oxidation (CWAO) of CV. The kind of metal had an important contribution in the redox process as significant differences were observed between Fe, Ni, and their mixtures. The catalysts with only Fe as active phase were more efficient for the oxidation of CV under normal conditions (T = 25 °C and atmospheric pressure) compared to those containing Ni, revealing the influence of the transition metal on catalytic properties. It was found that iron-containing materials displayed enhanced textural properties. The synthesis of Fe/MgAl catalysts by the autocombustion method led to solids with excellent catalytic behavior, 100% CV degradation in eight hours of reaction, 68% selectivity to CO₂, and significant reduction of chemical oxygen demand (COD).
Price Cameron, Pastor-Pérez L, Le Saché Estelle, Sepúlveda-Escribano A, Ramirez Reina Tomas (2017)Highly active Cu-ZnO catalysts for the WGS reaction at medium-high space velocities: effect of the support composition, In: International Journal of Hydrogen Energy42(16)pp. 10747-10751 Elsevier
Cu-ZnO based catalysts are the benchmark materials for the low-temperature WGS reaction. However, they present a crucial drawback which limits their application in portable devices: they only work under very low space velocities. In this study, we have developed a series of multicomponent Cu-ZnO catalysts able to work at relatively high space velocities with outstanding activity and stability. Different reference supports have been utilised with CeO2-Al2O3 being the most promising system. Overall, this work describes a strategy to design advanced Cu-based catalysts that can overcome the residence time restrictions in the WGS reaction.
Ramirez Reina Tomas, Pastor Perez Laura, Ivanova S, Centeno MA, Odriozola JA, Sepulveda-Escribano A (2015)Ni/CeO2/C catalysts with enhanced OSC for the WGS reaction, In: Catalysts5(1)pp. 298-309 MDPI AG
In this work, the WGS performance of a conventional Ni/CeO2 bulk catalyst is compared to that of a carbon-supported Ni-CeO2 catalyst. The carbon-supported sample resulted to be much more active than the bulk one. The higher activity of the Ni-CeO2/C catalyst is associated to its oxygen storage capacity, a parameter that strongly influences the WGS behavior. The stability of the carbon-supported catalyst under realistic operation conditions is also a subject of this paper. In summary, our study represents an approach towards a new generation of Ni-ceria based catalyst for the pure hydrogen production via WGS. The dispersion of ceria nanoparticles on an activated carbon support drives to improved catalytic skills with a considerable reduction of the amount of ceria in the catalyst formulation
Pastor-Perez Laura, Shah Mihir, Le Saché Estelle, Ramirez Reina Tomas (2018)Improving Fe/Al2O3 catalysts for the Reverse Water-Gas Shift reaction: on the effect of Cs as activity/selectivity promoter, In: Catalysts MDPI
Abstract: The conversion of CO2 into CO via the Reverse Water-Gas Shift (RWGS) reaction is a suitable route for CO2 valorisation. Fe-based catalysts are highly active for this reaction but their activity and selectivity can be substantially boosted by adding Cs as a promoter. In this work we demonstrate that Cs modifies the redox behaviour and the surface chemistry of the iron based materials. The metallic dispersion and the amount of metallic Fe centres available for the reaction depends on Cs loading. 5 wt.% of Cs is an optimum amount of dopant to achieve a fair activity/selective balance. Nevertheless, depending on the RWGS reactor operational temperature, lower concentrations of Cs also lead to acceptable catalytic performance. Along with the excellent activity of the prepared materials this work showcases their robustness for long-term runs and the strong impact of H2/CO ratio in the overall catalytic performance.
Centeno MA, Ramirez Reina T, Ivanova S, Laguna OH, Odriozola JA (2016)Au/CeO2 Catalysts: Structure and CO Oxidation Activity, In: Catalysts6(10)158 MDPI AG
In this comprehensive review, the main aspects of using Au/CeO2 catalysts in oxidation reactions are considered. The influence of the preparation methods and synthetic parameters, as well as the characteristics of the ceria support (presence of doping cations, oxygen vacancies concentration, surface area, redox properties, etc.) in the dispersion and chemical state of gold are revised. The proposed review provides a detailed analysis of the literature data concerning the state of the art and the applications of gold–ceria systems in oxidation reactions.
Boldrin P, Ruiz-Trejo E, Mermelstein J, Bermudez Menendez J, Ramirez Reina T, Brandon NP (2016)Strategies for carbon and sulfur tolerant solid oxide fuel cell materials, incorporating lessons from heterogeneous catalysis, In: Chemical Reviews
Solid oxide fuel cells (SOFCs) are a rapidly emerging energy technology for a low carbon world, providing high efficiency, potential to use carbonaceous fuels and compatibility with carbon capture and storage. However, current state-of-the-art materials have low tolerance to sulfur, a common contaminant of many fuels, and are vulnerable to deactivation due to carbon deposition when using carbon-containing compounds. In this review we first study the theoretical basis behind carbon and sulfur poisoning, before examining the strategies towards carbon and sulfur tolerance used so far in the SOFC literature. We then study the more extensive relevant heterogeneous catalysis literature for strategies and materials which could be incorporated into carbon and sulfur tolerant fuel cells.
Ramirez Reina T, Odriozola JA, Santos JL, Ivanova S, Centeno MA, Tabakova T, Idakiev V (2016)Gold Catalysts supported in CuO/ZnO/Al2O3, production method and use of thereof
Hurd Price C-A, Pastor-Pérez L, Ramirez Reina Tomas, Liu Jian (2018)Robust mesoporous bimetallic yolk-shell catalysts for chemical CO2 upgrading via dry reforming of methane, In: Reaction Chemistry & Engineering3pp. 433-436 Royal Society of Chemistry
Here, we report the synthesis of mesoporous ZnO/Ni@m-SiO2 yolk-shell particles. The unique ZnO/Ni@m-SiO2 catalysts demonstrate impressive resistance to sintering and coking for dry reforming of methane (DRM). They also display long term stability with high levels of conversion and selectivity, making this catalyst promising for chemical CO2 upgrading.
Pirou S, Bermudez JM, Vang Hendriksen P, Kaiser A, Ramirez Reina Tomas, Millan M, Kiebach R (2017)Stability and performance of robust dual-phase (ZrO2)0.89(Y2O3)0.01(Sc2O3)0.10-Al0.02Zn0.98O1.01 oxygen transport membranes, In: Journal of Membrane Science543pp. 18-27 Elsevier
Dual-phase composite oxygen transport membranes consisting of 50 vol% Al0.02Zn0.98O1.01 and 50 vol% (ZrO2)0.89(Y2O3)0.01(Sc2O3)0.10 were successfully developed and tested. The applicability of the membrane in oxy-fuel power plants schemes involving direct exposure to flue gas was evaluated by exposing the membrane to gas streams containing CO2, SO2, H2O and investigating possible reactions between the membrane material and these gases. The analyses of the exposed composites by x-ray diffraction (XRD), x-ray fluorescence (XRF), attenuated total reflection Fourier transform infrared spectroscopy (ATR-FTIR), and Raman spectroscopy revealed excellent stability. Additionally, an electrical conductivity measurement over 900 h confirmed that the composite is stable under prolonged exposure to CO2. However, an instability of the dual-phase membrane under oxygen partial pressures below PO2~10−4 atm. was found. Oxygen permeation tests on a 1 mm thick self-standing membrane resulted in an oxygen flux of 0.33 mLN min−1 cm−2 at 925 °C in air/N2. Stability tests in CO2 with 3 vol% O2 demonstrated the potential for the use of 10Sc1YSZ-AZO dual-phase membranes in oxy-combustion processes involving direct exposure to flue gas.
Jin Wei, Pastor- Pérez Laura, Shen DeKui, Sepúlveda-Escribano Antonio, Gu Sai, Ramirez Reina Tomas Catalytic upgrading of biomass model compounds: Novel approaches and lessons learnt from traditional hydrodeoxygenation - a review, In: ChemCatChem11(3)pp. 924-960 Wiley
Catalytic hydrodeoxygenation (HDO) is a fundamental process for bio-resources upgrading to produce transportation fuels or added value chemicals. The bottleneck of this technology to be implemented at commercial scale is its dependence on high pressure hydrogen, an expensive resource which utilization also poses safety concerns. In this scenario, the development of hydrogen-free alternatives to facilitate oxygen removal in biomass derived compounds is a major challenge for catalysis science but at the same time it could revolutionize biomass processing technologies. In this review we have analyzed several novel approaches, including catalytic transfer hydrogenation (CTH), combined reforming and hydrodeoxygenation, metal hydrolysis and subsequent hydrodeoxygenation along with non-thermal plasma (NTP) in order to avoid the supply of external H2. The knowledge accumulated from traditional HDO sets the grounds for catalysts and processes development among the hydrogen alternatives. In this sense, mechanistic aspects for HDO and the proposed alternatives are carefully analyzed in this work. Biomass model compounds are selected aiming to provide an indepth description of the different processes and stablish solid correlations catalysts composition-catalytic performance which can be further extrapolated to more complex biomass feedstocks. Moreover, the current challenges and research trends of novel hydrodeoxygenation strategies are also presented aiming to spark inspiration among the broad community of scientists working towards a low carbon society where bio-resources will play a major role.
Jin W., Pastor-Perez L., Villora-Picó Juan J., Sepúlveda-Escribano A., Gu S., Reina T. R. (2019)Investigating New Routes for Biomass Upgrading: “H2-Free” Hydrodeoxygenation Using Ni-Based Catalysts, In: ACS Sustainable Chemistry & Engineering7(19)pp. 16041-16049 American Chemical Society
This work showcases an innovative route for biocompound upgrading via hydrodeoxygenation (HDO) reactions, eliminating the need for external high-pressure hydrogen supply. We propose the use of water as reaction media and the utilization of multifunctional catalysts that are able to conduct multiple steps such as water activation and HDO. In this study, we validate our hypothesis in a high-pressure batch reactor process using guaiacol as a model compound and multicomponent Ni-based catalysts. In particular, a comparison between ceria-supported and carbon/ceria-supported samples is established, the carbon-based materials being the suitable choice for this reaction. The physicochemical study by X-ray photoelectron spectroscopy, transmission electron microscopy, X-ray diffraction, and temperature-programmed reduction reveals the greater dispersion of Ni clusters and the strong metal-support interaction in the carbon/ceria-based samples accounting for the enhanced performance. In addition, the characterization of the spent samples points out the resistance of our catalysts toward sintering and coking. Overall, the novel catalytic approach proposed in this paper opens new research possibilities to achieve low-cost bio-oil upgrading processes.
Ramirez Reina T, Santos JL, García-Moncada N, Ivanova S, Odriozola JA (2016)Development of Robust Mixed-Conducting Membranes with High Permeability and Stability, In: Granger P, Parvulescu VI, Kaliaguine S, Prellier W (eds.), Perovskites and Related Mixed Oxides: Concepts and Applications(32)pp. 719-738 Wiley
This chapter presents the current state of the art in the development of mechanically and chemically robust perovskite-based membranes for industrial applications. Without providing an exhaustive picture of all developments in the field, the principal points of interest are discussed and the most recent concepts summarized. Finally, brief guidelines for possible future studies are proposed.
Gozanlez M, Ramirez Reina T, Ivanova S, Centeno MA, Odriozola JA (2014)Pt vs. Au in water-gas shift reaction, In: Journal of Catalysis314pp. 1-1
This work presents a comparison of the gold- and platinum-based catalysts behavior in the water-gas shift (WGS) reaction. The influence of the support, e.g., its composition and electronic properties, studied in detail by means of UV-Vis spectroscopy, of the metal nature and dispersion and of the stream composition has been evaluated. The catalytic performance of the samples is directly correlated with the electronic properties modification as a function of metal and/or support. Both metals present high activity in the selected reaction although in a different operation temperature window.
Arbelaez O, Ramirez Reina T, Ivanova S, Bustamente F, Villa AL, Centeno MA, Odriozola JA (2015)Mono and bimetallic Cu-Ni structured catalysts for the water gas shift reaction, In: Applied Catalysis A: General497pp. 1-9
The water-gas shift (WGS) reaction over structured Cu, Ni, and bimetallic Cu-Ni supported on active carbon (AC) catalysts was investigated. The structured catalysts were prepared in pellets form and applied in the medium range WGS reaction. A good activity in the 180–350 °C temperature range was registered being the bimetallic Cu-Ni:2-1/AC catalyst the best catalyst. The presence of Cu mitigates the methanation activity of Ni favoring the shift process. In addition the active carbon gasification reaction was not observed for the Cu-containing catalyst converting the active carbon in a very convenient support for the WGS reaction. The stability of the bimetallic Cu-Ni:2-1/AC catalyst under continuous operation conditions, as well as its tolerance towards start/stop cycles was also evaluated.
Ramirez Reina T, Ivanova S, Centeno MA, Odriozola JA (2015)Boosting the activity of a Au/CeO2/Al2O3 catalysts for the WGS reaction, In: Catalysis Today253pp. 149-154
Herein a strategy to design highly efficient Au/CeO2/Al2O3 based WGS catalysts is proposed. The inclusion of transition metals, namely Fe, Cu and Zn as CeO2 dopant is considered. All the promoters successfully increased the WGS performance of the undoped sample. The activity improvement can be correlated to structural and/or redox features induced by the dopants. The comparative characterization of the doped samples by means of XRD, Raman spectroscopy and OSC evaluation permits an accurate understanding of the boosted WGS activity arising from the Ce-promoter interaction. This study establishes distinction among both, structural and redox sources of promotion and provides a useful strategy to develop highly active Au/CeO2 based catalysts for the WGS reaction.
Baena-Moreno Francisco M., Rodríguez-Galán Mónica, Vega Fernando, Reina T. R., Vilches Luis F., Navarrete Benito (2019)Converting CO2 from biogas and MgCl2 residues into valuable magnesium carbonate: A novel strategy for renewable energy production, In: Energy180pp. 457-464 Elsevier
In this work a novel strategy for bio-methane production and magnesium chloride waste valorization is addressed. The proposed process is a potential alternative path to the already existing biogas upgrading technologies by carbon dioxide mineralization into valuable magnesium carbonate. The main parameters affecting the precipitation efficiency (reaction time, reaction temperature, and molar ratio reactant/precipitator) are studied, leading to promising results which spark further investigation in this innovative route. Additionally the purity and the morphology of the obtained solid product was accurately analysed through different physicochemical characterization techniques such as Raman, X-Ray diffraction and Scanning electron microscope. The characterisation study reveals a mixture of Nesqueonite and Dypingite carbonate phases obtained in the process being the later the dominant phase in the resulting precipitate. Overall, the results discussed herein confirmed the technical feasibility of this innovative strategy for synergizing carbon dioxide mineralization and renewable energy production.
Ramirez Reina T, Ivanova S, Centeno MA, Odriozola JA (2015)Catalytic screening of Au/CeO2-MOx/Al2O3 catalysts (M= La,Ni,Cu,Fe,Cr,Y) in the CO-PrOx reaction, In: International Journal of Hydrogen Energy40(4)pp. 1782-1788
In this work, a series of Au/CeO2-MOx/Al2O3 catalysts has been prepared and evaluated in the PrOx reaction. Within the series of dopants Fe and Cu containing samples enhanced the catalytic performance of the parent Au/CeO2/Al2O3 catalyst being copper the most efficient promoter. For both samples an enhanced oxygen storage capacity (OSC) is registered and accounts for the high CO oxidation activity. More particularly, the Au/CeO2-CuOx/Al2O3 catalyst successfully withstands the inclusion of water in the PrOx stream and presents good results in terms of CO elimination. However to achieve a good selectivity toward CO2 formation properly adjusting of the reaction parameters, such as oxygen concentration and space velocity is needed. Within the whole screened series the Cu-containing catalyst can be considered as the most interesting alternative for H2 clean-up applications.
Baena-Moreno Francisco M., Pastor-Pérez Laura, Wang Qiang, Reina T.R. (2020)Bio-methane and bio-methanol co-production from biogas: A profitability analysis to explore new sustainable chemical processes, In: Journal of Cleaner Production265121909 Elsevier
Herein a potential synergy between biogas upgrading and CO2 conversion to bio-methanol is investigated. This novel idea arises as an alternative path to the traditional biogas – to – bio-methane route which involves CO2 separation. In this work a techno-economic analysis of the process was performed to study the profitability for potential investors. A total of 15 scenarios were analysed. Different biogas plant sizes were examined as baseline scenarios: 100, 250, 500, and 1000 m³/h. Furthermore the potential effect of governmental incentives through bio-methane subsidies (feed-in tariffs and investment percentage) was studied. Finally a sensitivity analysis was developed to study the effect of key parameters. The results of the baseline scenarios demonstrated that not profitable results can be obtained without subsidies. Bio-methane subsidies as feed-in tariffs proved to be effective for the 500 and 1000 m³/h plant sizes. For a feed-in tariff subsidy of 40 €/MW, 500 m³/h biogas production plants are remarkably profitable (net present value equal to 3106 k€). Concerning 1000 m³/h biogas production plants, 20 €/MW of subsidies as feed-in tariffs gives similar net present value result. Our results point out that only big biogas production can produce bio-methanol at profitable margins under 90–100% of investment subsidied. The sensitivity analysis showed that electricity, natural gas and bio-methanol price can affect considerably to the overall profitability, converting predicted positive cases in negative scenarios.
Baena‐Moreno Francisco M., Price Cameron Alexander Hurd, Le Saché Estelle, Pastor‐Pérez Laura, Sebastia Saez Daniel, Reina T. R. Physicochemical Comparison of Precipitated Calcium Carbonate for Different Configurations of a Biogas Upgrading Unit, In: Journal of Chemical Technology & Biotechnology94(7)pp. 2256-2262 Wiley

BACKGROUND

This paper presents a physicochemical comparison of the solid products obtained from two alternative processes that recycle waste sodium carbonate (Na2CO3) solution, which is produced following the absorption of CO2 in a biogas‐upgrading unit. Chemical regeneration processes offer an attractive alternative to the energetically demanding standard physical methods. In the first process, sodium hydroxide (NaOH) is regenerated as a precipitate from the chemical reaction of Na2CO3 with calcium hydroxide (Ca(OH)2). The second process shows a path to obtain a valuable sodium chloride (NaCl) and Calcium carbonate (CaCO3) rich brine from calcium chloride (CaCl2) acting as a precipitant agent. In both processes, Precipitated Calcium Carbonate (PCC) is obtained as the most valuable by‐product, but with varying properties due to the different origin.

RESULTS

The purpose of this work is to analyse physicochemically both variations of PCCs obtained and examining the differences between these solid samples in order to determine which method produces more desirable characteristics in the final product. To this end, FTIR, Raman, XRD and SEM were employed as characterization methods. The results reflect that both PCCs have a calcite crystal structure, or morph, being as both PCC products originate from CaCl2 that is more similar to commercial calcium carbonate calcite.

CONCLUSION

These results confirmed that a pure CaCO3 valuable by‐product can be obtained from a biogas upgrading unit with several industrial applications.

Ramirez Reina T, Ivanova S, Delgado JJ, Ivanov I, Tabakova T, Idakiev V, Centeno MA, Odriozola JA (2014)Viabilty of Au/CeO2-ZnO/Al2O3 catalysts for pure hydrogen production by the Water-Gas Shift reaction, In: ChemCatChem6(5)pp. 1401-1401
The production of H2 pure enough for use in fuel cells requires the development of very efficient catalysts for the water–gas shift reaction. Herein, a series of gold catalysts supported on ZnO-promoted CeO2–Al2O3 are presented as interesting systems for the purification of H2 streams through the water–gas shift reaction. The addition of ZnO remarkably promotes the activity of an Au/CeO2/Al2O3 catalyst. This increase in activity is mainly associated with the enhanced oxygen storage capacity exhibited for the Zn-containing solids. High activity and good stability and resistance towards start-up–shut-down situations was found, which makes these catalysts a promising alternative for CO clean-up applications.
Zhang Qi, Pastor-Perez L., Gu S., Ramirez Reina Tomas Transition Metal Carbides (TMCs) catalysts for gas phase CO2 upgrading reactions: a comprehensive overview, In: Catalysts MDPI
Increasing demand for CO2 utilization reactions and the stable character of CO2 have motivated the interest in developing highly active, selective and stable catalysts. Precious metal catalysts have been studied extensively due to their high activities, but their implementation for industrial applications is hindered due to their elevated cost. Among the materials which have comparatively low prices, transition metal carbides (TMCs) are deemed to display catalytic properties similar to Pt-group metals (Ru, Rh, Pd, Ir, Pt) in several reactions such as hydrogenation and dehydrogenation processes. In addition, they are excellent substrates to disperse metallic particles. Hence, the unique properties of TMCs make them ideal substitutes for precious metals resulting in promising catalysts for CO2 utilization reactions. This work aims to provide a comprehensive overview of recent advances on TMCs catalysts towards gas phase CO2 utilization processes, such as CO2 methanation, reverse water gas shift (rWGS) and dry reforming of methane (DRM). We have carefully analyzed synthesis procedures, performances and limitations of different TMCs catalysts. Insights on material characteristics such as crystal structure and surface chemistry and their connection with the catalytic activity are also critically reviewed.
Volpe R, Bermúdez Menendez JM, Ramirez Reina Tomas, Messineo A, Millan M (2017)Evolution of chars during slow pyrolysis of citrus waste, In: Fuel Processing Technology158pp. 255-263 Elsevier
Conversion of agro-wastes into energy can be key to a circular-driven economy that could lead tomodels for sustainable production. Thermochemical processing is an interesting alternative for the upgrading of agro-wastes to energy. However, owing to the complex and largely unknown set of reactions occurring during thermal breakdown, to ensuring consistent quality of the final products is still a goal to achieve at industrial level. The present study investigates the evolution of solid products of pyrolysis, to gain some insights in these complexities. Chars derived fromslowpyrolysis (200–650 °C) of citrus pulp in a horizontal reactor have been characterized bymeans of Fourier Transform Infrared spectroscopy (FT-IR), X-Ray Diffraction (XRD), ThermoGravimetric Analysis (TGA) and Scanning Electron Microscopy (SEM). Results are discussed also in light of similarities with coal thermal breakdown. At temperatures below 300 °C, changes in solid matrix are mainly due to breaking of aliphatic compounds. Significant changes in char structure and behavior then occur between 300 °C and 500 °C mainly related to secondary char-tar reactions. Above 500 °C, changes appear to occur mainly due to recombination reactions within matrix, which thereby becomes progressively less reactive.
Zhang Zhien, Baena-Moreno Francisco M., Vega Fernando, Pastor-Pérez Laura, Reina T.R., Navarrete Benito Novel Process for Carbon Capture and Utilization and Saline Wastes Valorization, In: Journal of Natural Gas Science and Engineering103071 Elsevier
Herein a novel process for CO₂ capture and utilization suitable for small-medium scale applications is presented. The use of potassium and calcium wastes is proposed as an alternative low-energy path to CO₂ capture and waste valorization. In our work, CaCO₃ precipitation studies were performed to corroborate the feasibility of the novel process described. Reaction time, reaction temperature, molar ratio, and K₂CO₃ initial concentration were varied to analyse their effects on the precipitation efficiency. The purity and main characteristics of the obtained product were physicochemically characterized to evaluate the potential cost of the final solid product by means of Raman spectroscopy, X-ray diffraction, FTIR, and scanning electron microscopy. Results show that promising precipitation efficiencies are obtained in comparison with other waste-valorization and CO₂ capture process, even at room temperatures. High quality calcite was obtained as solid product. Overall our work confirms the technical viability of the proposed route to synergize CO₂ capture and saline waste utilization.
The development of catalytic materials for the recycling CO2 through a myriad of available processes is an attractive field, especially given the current climate change. While there is increasing publication in this field, the reported catalysts rarely deviate from the traditionally supported metal nanoparticle morphology, with the most simplistic method of enhancement being the addition of more metals to an already complex composition. Encapsulated catalysts, especially yolk@shell catalysts with hollow voids, offer answers to the most prominent issues faced by this field, coking and sintering, and further potential for more advanced phenomena, for example, the confinement effect, to promote selectivity or offer greater protection against coking and sintering. This work serves to demonstrate the current position of catalyst development in the fields of thermal CO2 reforming and hydrogenation, summarizing the most recent work available and most common metals used for these reactions, and how yolk@shell catalysts can offer superior performance and survivability in thermal CO2 reforming and hydrogenation to the more traditional structure. Furthermore, this work will briefly demonstrate the bespoke nature and highly variable yolk@shell structure. Moreover, this review aims to illuminate the spatial confinement effect and how it enhances yolk@shell structured nanoreactors is presented.
Ramirez Reina Tomas, Moreno Francisco Manuel Baena Profitability analysis of a novel configuration to synergize Biogas Upgrading and Power-to-Gas", In: Energy Conversion and Management Elsevier
Gonzalez-Castano M, Ramirez Reina T, Ivanova S, Martinez-Tejada M, Centeno MA, Odriozola JA (2016)O2-assisted Water Gas Shift reaction using Au and Pt structured catalysts, In: Applied Catalysis B: Environmental185pp. 337-343 Elsevier
Platinum and gold structured catalysts were compared as active phases in classical and O2-assisted Water Gas Shift (WGS) reaction. Both metals were supported on iron-doped ceria mixed oxide and then, structured on metallic micromonolithic devices. As expected the WGS activity of both micromonoliths is conditioned by the nature of the noble metals being Pt the most active metal in traditional conditions. However, the addition of oxygen to the classical water gas feed turns the balance in favor of the gold based catalysts, being the presence of gold responsible for an excessive improvement of the catalytic activity
Santos JL, Ramirez Reina Tomas, Ivanova S, Centeno MA, Odriozola JA (2017)Gold promoted Cu/ZnO/Al2O3 catalysts prepared from hydrotalcite precursors: Advanced materials for the WGS reaction, In: Applied Catalysis B: Environmental201pp. 310-317
Outstanding catalysts for the water was shift reaction are reported in this work. The combination of gold nanoparticles with Cu/ZnO/Al2O3 prepared from hydrotalcite-like precursors leads to very promising systems for pure hydrogen production. Full CO conversion is reached at temperatures as low as 180 °C. The key point seems to be the cooperation of Au and Cu and the optimal metal-oxide contact derived from the synthesis method. The high activity of gold for low temperature CO oxidation and the suitability of copper for the WGS results in a perfect synergy. Moreover the materials developed in this work present good stability and tolerance towards start/stop cycles an indispensable requisite for a realistic application in an integrated hydrogen fuel processor.
Unal I, Meisuria S, Choolaei Mohammadmehdi, Ramirez Reina Tomas, Amini Horri Bahman (2018)Synthesis and Characteristics of Nanocrystalline Ni1-xCoxO/GDC Powder as a Methane Reforming Catalyst for SOFCs, In: Ceramics International44(6)pp. 6851-6860 Elsevier
This paper has described the application of nickel-doped catalytic constituents based on gadolinium-doped ceria (GDC) for fabrication of the solid-oxide fuel cell (SOFC) anode layer integrated with an in-situ methane-reforming layer (MRL). Nanocrystalline powders of Ni1-xCo3xO1+3x/GDC and Ni1-xCuxO/GDC with various compositions (x = 0.3, 0.5, 0.7) were synthesised using an ultrasound-assisted method followed by a thermal treatment to be applied for fabrication of the integrated MRL and the SOFC anode layer, respectively. Thermogravimetric analysis showed that the synthesized powders should be optimally calcined at 700 °C to exhibit improved crystallinity and catalytic activity. The morphological analysis showed the formation of nanocrystalline powders with particle size ranging from 4-86 nm that was confirmed by the crystal size analysis using XRD results. The elemental analysis by EDX indicated a successful distribution of the constituent ceramic and bimetallic phases after the addition of a sonication stage. The results of FT-IR and Raman spectroscopy confirmed lack of solvents residual after calcination that was in agreement with residual moisture content values obtained from TGA data. The fabricated anode-MRL bilayers had an adequate porosity (36.7%) and shrinkage (33.5%) after adding carbon particles as a pore former (at a loading fraction of 5.9 wt.%). The catalytic performance measurements of the MRL showed a methane conversion of 13% at maximum activity with a weight hour space velocity (WHSV) of 60 L/gh that was mainly due to carbon deposition in the reaction condition.
Price Cameron Alexander Hurd, Ramirez Reina Tomas, Liu Jian (2020)Engineering heterogenous catalysts for chemical CO₂ utilization: Lessons from thermal catalysis and advantages of yolk@shell structured nanoreactors, In: Journal of Energy Chemistry Elsevier
The development of catalytic materials for the recycling CO₂ through a myriad of available processes is an attractive field, especially given the current climate change. While there is increasing publication in this field, the reported catalysts rarely deviate from the traditionally supported metal nanoparticle morphology, with the most simplistic method of enhancement being the addition of more metals to an already complex composition. Encapsulated catalysts, especially yolk@shell catalysts with hollow voids, offer answers to the most prominent issues faced by this field, coking and sintering, and further potential for more advanced phenomena, for example, the confinement effect, to promote selectivity or offer greater protection against coking and sintering. This work serves to demonstrate the current position of catalyst development in the fields of thermal CO₂ reforming and hydrogenation, summarizing the most recent work available and most common metals used for these reactions, and how yolk@shell catalysts can offer superior performance and survivability in thermal CO₂ reforming and hydrogenation to the more traditional structure. Furthermore, this work will briefly demonstrate the bespoke nature and highly variable yolk@shell structure. Moreover, this review aims to illuminate the spatial confinement effect and how it enhances yolk@shell structured nanoreactors is presented.
Ramirez Reina T, González Castaño M, Palma S, Ivanova S (2014)Twenty Years of Golden Future in the Water Gas Shift Reaction, In: Ma Z, Dai S (eds.), Heterogeneous Gold Catalysts and Catalysis18(5)pp. 111-139 Royal Society of Chemistry
Once considered an inert element, gold has recently gained attention as a catalyst. This book presents a comprehensive review of this rapidly-evolving field. It provides readers with a thorough background to the use of gold in catalysis, as well as the latest methods for the preparation of gold catalysts. Written to be accessible by postgraduates and newcomers to the field, this book is also beneficial to experienced researchers and is an essential reference in the laboratory.
Ramirez Reina T, Xu W, Ivanova S, Centeno MA, Hanson J, Rodriguez JA, Odriozola JA (2012)Operando characterization of iron-promoted ceria-alumina gold catalysts during the water-gas shift reaction
Baena Francisco, Sebastia Saez Juan Daniel, Wang Qiang, Ramirez Reina Tomas Is the production of biofuels and bio-chemicals always profitable? Co-production of biomethane and urea from biogas as case study., In: Energy Conversion and Management Elsevier
In this paper we present a techno-economic analysis of a novel route for biomethane – urea co-production from biogas. The idea emerges as an alternative path for improving the profitability of biogas upgrading plants. The profitability of four different biogas plant sizes (100, 250, 500, and 1000 m3/h) in four European countries (Spain, Italy, United Kingdom and Germany) is studied under the current policy schemes for biomethane production of each country. Our study evidences that with the present policy schemes for biomethane production, only medium and large scale plants (500 and 1000 m3/h) in Italy would be profitable. The reason is the current strong support for biomethane production in Italy through feed-in tariffs subsidies. In this sense, we analysed the potential benefits of governmental incentives through bio-methane subsidies (feed-in tariffs and investment percentage). Feed-in tariffs proved to be a worthwhile solution for large plants. Indeed, profitability is reached under subsidies of 30-48 €/MWh. Overall, plants located in southern EU countries are more likely to reach profitability with lower subsidies. The potential of costs reduction (i.e. ammonia price) was also analysed, showing that cutting-down production costs is essential to reduce the amount of subsidies received. In summary, our study shows the challenge that European policies face in the path towards a bio-based economy using biogas upgrading as reference case.
Millan M, Ramirez Reina T, Bermudez JM, Puron H, Pinilla JL (2016)CATALYST FOR PROCESSING HEAVY OILS AND ITS PREPARATION METHOD
Baena-Moreno Francisco, Rodríguez-Galán Mónica, Vega Fernando, Reina T., Vilches Luis, Navarrete Benito (2018)Regeneration of Sodium Hydroxide from a Biogas Upgrading Unit through the Synthesis of Precipitated Calcium Carbonate: An Experimental Influence Study of Reaction Parameters, In: Processes6(11) MDPI
This article presents a regeneration method of a sodium hydroxide (NaOH) solution from a biogas upgrading unit through calcium carbonate (CaCO3) precipitation as a valuable by-product, as an alternative to the elevated energy consumption employed via the physical regeneration process. The purpose of this work was to study the main parameters that may affect NaOH regeneration using an aqueous sodium carbonate (Na2CO3) solution and calcium hydroxide (Ca(OH)2) as reactive agent for regeneration and carbonate slurry production, in order to outperform the regeneration efficiencies reported in earlier works. Moreover, Raman spectroscopy and Scanning Electron Microscopy (SEM) were employed to characterize the solid obtained. The studied parameters were reaction time, reaction temperature, and molar ratio between Ca(OH)2 and Na2CO3. In addition, the influence of small quantities of NaOH at the beginning of the precipitation process was studied. The results indicate that regeneration efficiencies between 53%–97% can be obtained varying the main parameters mentioned above, and also both Raman spectroscopy and SEM images reveal the formation of a carbonate phase in the obtained solid. These results confirmed the technical feasibility of this biogas upgrading process through CaCO3 production.
Pastor Perez Laura, Le Saché Estelle, Jones C., Gu Sai, Arellano-Garcia Harvey, Ramirez Reina Tomas (2017)Synthetic natural gas production from CO 2 over Ni-x/CeO 2 -ZrO 2 (x = Fe, Co) catalysts: Influence of promoters and space velocity, In: Catalysis Today317pp. 108-113 Elsevier
Herein, the production of synthetic natural gas is proposed as an effective route for CO2 conversion. Typical catalysts for this reaction are based on Ni. In this study, we demonstrated that the addition of promoters such as iron and cobalt can greatly benefit the activity of standard Ni methanation catalysts. In particular cobalt seems to be a very efficient promoter. Our Co doped material is an outstanding catalysts for the CO2 methanation leading to high levels of CO2 conversion with selectivities close to 100%. Additionally, this catalyst is able to preserve excellent performance at relatively high space velocity which allows flexibility in the reactor design making easier the development of compact CO2 utilisation units. As an additional advantage, the Co-promoted catalysts is exceptionally stable conserving high levels of CO2 conversion under continuous operations in long terms runs.
Ramirez Reina Tomas, Guharoy Utsab, Olsson Emilia, Gu Sai, Cai Qiong Theoretical insights of Ni2P (0001) surface towards its potential applicability in CO2 conversion via dry reforming of methane, In: ACS Catalysis9(4)pp. 3487-3497 American Chemical Society
This study reports the potential application of Ni2P as highly effective catalyst for chemical CO2 recycling via dry reforming of methane (DRM). Our DFT calculations reveal that the Ni2P (0001) surface is active towards adsorption of the DRM species, with the Ni hollow site being the most energetically stable site and Ni-P and P contributes as co-adsorption sites in DRM reaction steps. Free energy analysis at 1000 K found CH-O to be the main pathway for CO formation. The competition of DRM and reverse water gas shift (RWGS) is also evidenced with the latter becoming important at relatively low reforming temperatures. Very interestingly oxygen seems to play a key role in making this surface resistant towards coking. From microkinetic analysis we have found greater oxygen surface coverage than that of carbon at high temperatures which may help to oxidize carbon deposits in continuous runs. The tolerance of Ni2P towards carbon deposition was further corroborated by DFT and micro kinetic analysis. Along with the higher probability of C oxidation we identify poor capacity of carbon diffusion on the Ni2P (0001) surface with very limited availability of C nucleation sites. Overall, this study opens new avenues for research in metal-phosphide catalysis and expands the application of these materials to CO2 conversion reactions.
Liu Xiaoyan, Lan Guojun, Su Panpan, Qian Lihua, Ramirez Reina Tomas, Wang Liang, Li Ying, Liu Jian Highly stable Ru nanoparticles incorporated in mesoporous carbon catalysts for production of γ-valerolactone, In: Catalysis Today Elsevier
The hydrogenation of levulinic acid to γ-valerolactone with water as solvent is a crucial reaction for producing fine chemicals. However, the development of highly stable catalysts is still a major challenge. Here, we prepared a Ru nanoparticles incorporated in mesoporous-carbon (Ru-MC) catalyst to achieve high stability in acidic aqueous medium. The Ru-MC showed excellent catalytic performance (12024h-1 turnover frequency) in the hydrogenation of LA-to3 GVL. Compared with Ru supported on mesoporous carbon catalyst (Ru/MC) prepared by conventional wet impregnation method, the Ru-MC showed excellent reusability (more than 6 times) and thermal stability (up to 600 oC). Based on H2-TPR-MS characterization, it was proposed that the incorporated structure significantly increased the interaction between Ru nanoparticles and carbon support, which effectively prevent the leaching and sintering of Ru nanoparticles and contributed to increased high reusability and thermal stability of the Ru-MC.
Yu J., Odriozola J.A., Gu S., Reina T.R, Jin Wei, Pérez L. Pastor- Cost-effective routes for Catalytic Biomass Upgrading, In: Current Opinion in Green and Sustainable Chemistry
Catalytic hydrodeoxygenation (HDO) is a fundamental and promising route for bio-oil upgrading to produce petroleum-like hydrocarbon fuels or chemical building blocks. One of the main challenges of this technology is the demand of high-pressure H2, which poses high costs and safety concerns. Accordingly, developing cost-effective routes for biomass or bio-oil upgrading without the supply of commercial H2 is essential to implement the HDO at commercial scale. This paper critically reviewed the very recent studies relating to the novel strategies for upgrading the bio-feedstocks with ‘green’ H2 generated from renewable sources. More precisely, catalytic transfer hydrogenation/hydrogenolysis (CTH), combined reforming and HDO, combined metal hydrolysis and HDO, water-assisted in-situ HDO and non-thermal plasma (NTP) technology and self-supported hydrogenolysis (SSH) are reviewed herein. Current challenges and research trends of each strategy are also proposed aiming to motivate further improvement of these novel routes to become competitive alternatives to conventional HDO technology.
Rood Shawn C., Ahmet Huseyin B., Gomez-Ramon Anais, Torrente-Murciano Laura, Reina Tomas R., Eslava Salvador (2018)Enhanced Ceria Nanoflakes using Graphene Oxide as a Sacrificial Template for CO Oxidation and Dry Reforming of Methane, In: Applied Catalysis B: Environmental242pp. 358-368 Elsevier
The development of novel fabrication methods to produce ceria catalysts with good high-temperature stability is critical for their implementation across a range of different applications. Herein, graphene oxide flakes are used as a sacrificial template in the synthesis of ceria particles to replicate the graphene oxide’s two-dimensionality. While performing the synthesis without graphene oxide results in large agglomerations of ceria crystallites, the addition of graphene oxide during the synthesis results in ceria nanoflakes (< 10 nm) replicating the graphene oxide morphology. This novel shape limits the diffusion of atoms at high temperature to a two-dimensional plane which is translated into a low sintering degree and consequently, an enhanced thermal stability. In this way, the ceria flakes are capable of maintaining high surface areas after calcination at high temperatures (> 400 °C) which results in improved catalytic performance for the oxidation of carbon monoxide. This resistance versus sintering has also a beneficial effect when ceria flakes are used as catalytic support of nickel particles. Improved metal dispersion and high metal-support interaction leads to lower sintering during the dry reforming of methane than similarly prepared un-templated ceria nickel catalysts. These results demonstrate the advantage of using graphene oxide as a sacrificial template for the production of sintering-resistant catalysts with good catalytic performance at high temperatures.
le Saché E., Santos J.L., Smith T.J., Arellano-Garcia Harvey, Odriozola J.A., Ramirez Reina Tomas (2018)Multicomponent Ni-CeO2 Nanocatalysts for Syngas production from CO2/CH4 mixtures, In: Journal of CO2 Utilization25pp. 68-78 Elsevier
The dry reforming of methane with CO2 is a common route to transform CO2/CH4 mixtures into added value syngas. Ni based catalysts are highly active for this goal but suffer from deactivation, as such promoters need to be introduced to counteract this, and improve performance. In this study, mono- and bi-metallic formulations based on 10 wt.% Ni/CeO2-Al2O3 are explored and compared to a reference 10 wt.% Ni/γ-Al2O3. The effect of Sn and Pt as promoters of Ni/CeO2-Al2O3 was also investigated. The formulation promoted with Sn looked especially promising, showing CO2 conversions stabilising at 65% after highs of 95%. Its increased performance is attributed to the additional dispersion Sn promotion causes. Changes in the reaction conditions (space velocity and temperature) cement this idea, with the Ni-Sn/CeAl material performing superiorly to the mono-metallic material, showing less deactivation. However, in the long run it is noted that the mono-metallic Ni/CeAl performs better. As such the application is key when deciding which catalyst to employ in the dry reforming process.
Odriozola JA, Ramirez Reina T, Centeno MA, Ivanova A, Idakiev V, Tabakova T (2013)Gold catalysts and the use thereof in the water-gas shift reaction
The present invention relates to a substrate for a gold catalyst, of formula CeO2 - ΜΟχ/ΑΙ2O3, wherein the substrate comprises between 60 and 90% w/w of Al2O3 and a percentage of CeO2 between 10 and 40% w/w, optionally doped with MOx oxide, with M selected from Fe, Zn, Co and Ni, Zr or mixtures thereof. The present invention relates to the use of the catalyst for the water-gas shift reaction and, more particularly, the use thereof in fuel cells.
Jin Wei, Pastor-Pérez Laura, Villora-Pico Juan J., Pastor-Blas Mercedes M., Sepúlveda-Escribano Antonio, Gu Sai, Charisiou Nikolaos D., Papageridis Kyriakos, Goula Maria A., Reina Tomas R. (2019)Catalytic Conversion of Palm Oil to Bio-Hydrogenated Diesel over Novel N-Doped Activated Carbon Supported Pt Nanoparticles, In: Energies13(1) MDPI
Bio-hydrogenated diesel (BHD), derived from vegetable oil via hydrotreating technology, is a promising alternative transportation fuel to replace nonsustainable petroleum diesel. In this work, a novel Pt-based catalyst supported on N-doped activated carbon prepared from polypyrrole as the nitrogen source (Pt/N-AC) was developed and applied in the palm oil deoxygenation process to produce BHD in a fixed bed reactor system. High conversion rates of triglycerides (conversion of TG > 90%) and high deoxygenation percentage (DeCOx% = 76% and HDO% = 7%) were obtained for the palm oil deoxygenation over Pt/N-AC catalyst at optimised reaction conditions: T = 300 ◦C, 30 bar of H2, and LHSV = 1.5 h−1 . In addition to the excellent performance, the Pt/N-AC catalyst is highly stable in the deoxygenation reaction, as confirmed by the XRD and TEM analyses of the spent sample. The incorporation of N atoms in the carbon structure alters the electronic density of the catalyst, favouring the interaction with electrophilic groups such as carbonyls, and thus boosting the DeCOx route over the HDO pathway. Overall, this work showcases a promising route to produce added value bio-fuels from bio-compounds using advanced N-doped catalysts.
Guharoy Utsab, Le Saché Estelle, Cai Qiong, Ramirez Reina Tomas, Gu Sai (2018)Understanding the role of Ni-Sn interaction to design highly effective CO2 conversion catalysts for dry reforming of methane, In: Journal of CO2 Utilization27pp. 1-10 Elsevier
CO2 reforming of methane is an effective route for carbon dioxide recycling to valuable syngas. However conventional catalysts based on Ni fail to overcome the stability requisites in terms of resistance to coking and sintering. In this scenario, the use of Sn as promoter of Ni leads to more powerful bimetallic catalysts with enhanced stability which could result in a viable implementation of the reforming technology at commercial scale. This paper uses a combined computational (DFT) and experimental approach, to address the fundamental aspects of mitigation of coke formation on the catalyst’s surface during dry reforming of methane (DRM). The DFT calculation provides fundamental insights into the DRM mechanism over the mono and bimetallic periodic model surfaces. Such information is then used to guide the design of real powder catalysts. The behaviour of the real catalysts mirrors the trends predicted by DFT. Overall the bimetallic catalysts are superior to the monometallic one in terms of long-term stability and carbon tolerance. In particular, low Sn concentration on Ni surface effectively mitigate carbon formation without compromising the CO2 conversion and the syngas production thus leading to excellent DRM catalysts. The bimetallic systems also presents higher selectivity towards syngas as reflected by both DFT and experimental data. However, Sn loading has to be carefully optimized since a relatively high amount of Sn can severely deter the catalytic performance.
Baena-Moreno Francisco M., Rodríguez-Galán Mónica, Reina T. R., Zhang Zhien, Vilches Luis F., Navarrete Benito (2019)Understanding the effect of Ca and Mg ions from wastes in the solvent regeneration stage of a biogas upgrading unit, In: Science of the Total Environment691pp. 93-100 Elsevier
This paper reveals the effect of calcium and magnesium ions in carbonation experiments carried out to regenerate sodium hydroxide from a biogas upgrading unit. This novel study arises as an alternative to standard physical process whose elevated energy consumption imposes economic restrictions. Previous works employed alkaline waste to turn them into value added product. Nevertheless, no attractive economical results were obtained due to the low regeneration efficiencies. Our hypothesis is that both calcium and magnesium waste composition percentages have an impact in the result, hence this work propose an isolated study aiming to determine the of each one in the global performance. To this end, the operational parameters (reaction time, reaction temperature and molar ratio) were tuned as well as physicochemical properties of the final solid samples were analysed by several techniques. The results indicate that calcium is much more prone than magnesium to reach high efficiencies in aqueous carbonation experiments. Additionally, higher quality products were achieved with calcium. The results of this study suppose an important step for understanding the aqueous carbonation through waste in the path to achieve a more sustainable city and society.
Katranidis Vasileios, Gu Sai, Ramirez Reina Tomas, Alpay Esat, Allcock B, Kamnis S (2017)Experimental study of high velocity oxy-fuel sprayed WC-17Co coatings applied on complex geometries. Part B: Influence of kinematic spray parameters on microstructure, phase composition and decarburization of the coatings, In: Surface and Coatings Technology328pp. 499-512 Elsevier
The aim of this study is to evaluate comprehensively the effect of spray angle, spray distance and gun traverse speed on the microstructure and phase composition of HVOF sprayed WC-17 coatings. An experimental setup that enables the isolation of each one of the kinematic parameters and the systemic study of their interplay is employed. A mechanism of particle partition and WC-cluster rebounding at short distances and oblique spray angles is proposed. It is revealed that small angle inclinations benefit notably the WC distribution in the coatings sprayed at long stand-off distances. Gun traverse speed, affects the oxygen content in the coating via cumulative superficial oxide scales formed on the as-sprayed coating surface during deposition. Metallic W continuous rims are seen to engulf small splats, suggesting crystallization that occurred in-flight.
Ramirez Reina T, Yeletski P, Bermudez JM, Arcelus-Arrillaga P, Yakovlev VA, Millan M (2015)Anthracene Aquacracking Using NiMo/SiO2 Catalysts in Supercritical Water Conditions, In: Proceddings of 2015 AIChE Annual Meeting
The current status of world oil reserves is a contentious matter, but it is widely accepted that conventional resources are dwindling and their reserves are less easily accessible [1]. Therefore, the production of heavy crude oil (HCO), which is the remnant of conventional oil has become more relevant and will remain so in the foreseeable future [2]. In this sense, there is a need for more efficient refining processes to transform HCO into lighter fuels. Conventional processes for increasing the value of heavy oil fractions aim to increase the H/C ratio of fuel, generating lighter fractions. However, this implies either rejecting a large amount of the carbon in the feed as in thermal and catalytic cracking processes, or using high pressure hydrogen, an expensive gas, in hydrocracking processes [3].
Le Saché Estelle, Johnson Sarah, Pastor-Pérez Laura, Amini Horri Bahman, Reina Tomas (2019)Biogas Upgrading Via Dry Reforming Over a Ni-Sn/CeO2-Al2O3 Catalyst: Influence of the Biogas Source, In: Energies12(6) MDPI
Biogas is a renewable, as well as abundant, fuel source which can be utilised in the production of heat and electricity as an alternative to fossil fuels. Biogas can additionally be upgraded via the dry reforming reactions into high value syngas. Nickel-based catalysts are well studied for this purpose but have shown little resilience to deactivation caused by carbon deposition. The use of bi-metallic formulations, as well as the introduction of promoters, are hence required to improve catalytic performance. In this study, the effect of varying compositions of model biogas (CH4/CO2 mixtures) on a promising multicomponent Ni-Sn/CeO2-Al2O3 catalyst was investigated. For intermediate temperatures (650 °C), the catalyst displayed good levels of conversions in a surrogate sewage biogas (CH4/CO2 molar ratio of 1.5). Little deactivation was observed over a 20 h stability run, and greater coke resistance was achieved, related to a reference catalyst. Hence, this research confirms that biogas can suitably be used to generate H2-rich syngas at intermediate temperatures provided a suitable catalyst is employed in the reaction.
Baena-Moreno Francisco M., Rodríguez-Galán Mónica, Vega Fernando, Reina T. R., Vilches Luis F., Navarrete Benito (2019)Understanding the Influence of the Alkaline Cation K+ or Na+ in the Regeneration Efficiency of a Biogas Upgrading Unit, In: International Journal of Energy Research43(4)pp. 1578-1585 Wiley
This paper reveals a regeneration method for a carbonate compound after carbon dioxide (CO2) absorption in a biogas upgrading unit run with caustic mixtures, obtaining precipitated calcium carbonate (PCC) as valuable by-product. This process arises as an alternative to physical regeneration, which is highly energy intensive. This work provides novel insights on the regeneration efficiency of carbonates to hydroxides while also studying the influence of K+ or Na+ in the caustic CO2-trapping solution. The compared parameters were the reaction time, temperature and molar ratio. Moreover, psychochemical characterization of solids was obtained by means of Fourier-transform infrared spectroscopy (FTIR), Raman spectroscopy, X-ray powder diffraction (XRD) and Scanning Electron Microscopy (SEM) images. The results indicate that regeneration efficiencies are slightly lower when potassium is used instead of sodium, but quite acceptable for both of them. The chemical characterization experiments showed the predominance of calcium carbonate. Overall, the results obtained in this study proved that this process is feasible to upgrade biogas through PCC precipitation, which appears to be a promising economically viable process to synergise CCS and CCU.
Ramirez Reina T, Papadopoulou E, Palma S, Ivanova S, Centeno MA, Ioannides T, Odriozola JA (2014)Could an efficient WGS catalyst be useful in the CO-PrOx reaction?, In: Applied Catalysis B: Environmental150pp. 554-563
This work presents an evaluation of a high performance series of water gas shift (WGS) catalysts in the preferential CO oxidation reaction (PrOx) in order to examine the applicability of the same catalyst for both processes as a first step for coupling both reactions in a single process. Gold based catalysts are applied in an extensive study of the CO-PrOx reaction parameters, such as λ, WHSV, CO concentration and [H2O]/[CO2] ratio in order to obtain the best activity/selectivity balance. CO and H2 oxidation reactions were treated separately in order to establish the degree of CO/H2 oxidation competition. Additionally the catalysts behavior in the CO-PrOx parallel reactions such a WGS and RWGS have been also carried out to analyze their effect on product composition.
Ketabchi Elham, Pastor Perez Laura, Ramirez Reina Tomas, Arellano-Garcia Harvey (2019)Catalytic upgrading of acetone, butanol and Ethanol (ABE): A step ahead for the production of added value chemicals in bio-refineries, In: ACS Sustainable Chemistry and Engineering American Chemical Society
Ramirez Reina Tomas, Pastor Perez Laura, Patel V, Le Saché Estelle CO2 methanation in the presence of methane: catalysts design and effect of methane concentration in the reaction mixture, In: Journal of the Energy Institute Elsevier
The work in this paper evidences the viability of producing synthetic natural gas (SNG) via the methanation reaction tackling two fundamental challenges on methanation catalysis (i) the development of advanced catalysts able to achieve high CO2 conversion and high methane yields and (ii) the unexplored effect of residual methane on the methanation stream. Both challenges have been successfully addressed using Ni/CeO2-ZrO2 catalysts promoted with Mn and Co. Mn does not seem to be a good promoter while Co prevents carbon deposition and secondary reactions. In fact, our Co-doped sample reached high levels of CO2 conversion and CH4 selectivity, especially at low reaction temperatures. In addition, this catalyst exhibits excellent catalytic behaviour when methane is introduced into the gas mixture, indicating its feasibility for further study to be conducted in realistic flue gases environments and methanation units with recycling loops. Furthermore, when methane is introduced in the reactant mixture, the Ni-Co/CeO2-ZrO2 sample is very stable maintaining high levels of conversion and selectivity. Overall our Co-doped catalyst can deliver high purity synthetic natural gas for long-term runs, promising results for gas-phase CO2 conversion units.
Yang Liuqingqing, Pastor Perez Laura, Villora-Pico J.J, Gu Sai, Sepúlveda-Escribano A., Ramirez Reina Tomas CO2 valorisation via Reverse Water-Gas Shift reaction using promoted Fe/CeO2-Al2O3 catalysts: showcasing the potential of advanced catalysts to explore new processes design, In: APPLIED CATALYSIS A-GENERAL593117442 ELSEVIER SCIENCE BV
The RWGS reaction represents a direct approach for gas-phase CO2 upgrading. This work showcases the efficiency of Fe/CeO2-Al2O3 catalysts for this process, and the effect of selected transition metal promoters such as Cu, Ni and Mo. Our results demonstrated that both Ni and Cu remarkably improved the performance of the monometallic Fe-catalyst. The competition Reverse Water-Gas Shift (RWGS) reaction/CO2 methanation reaction was evident particularly for the Ni-catalyst, which displayed high selectivity to methane in the low-temperature range. Among the studied catalysts the Cu promoted sample represented the best choice, exhibiting the best activity/selectivity balance. In addition, the Cu-doped catalyst was very stable for long-term runs – an essential requisite for its implementation in flue gas upgrading units. This material can effectively catalyse the RWGS reaction at medium-low temperatures, providing the possibility to couple the RWGS reactor with a syngas conversion reaction. Such an integrated unit opens the horizons for a direct CO2 to fuels/chemicals approach.
Ye Run-Ping, Liao Lin, Ramirez Reina Tomas, Liu Jiaxu, Chevella Durgaiah, Jin Yonggang, Fan Maohong, Liu Jian (2021)Engineering Ni/SiO₂ catalysts for enhanced CO₂ methanation, In: Fuel285119151 Elsevier
The CO₂ methanation is an important process in coal-to-gas, power-to-gas and CO₂ removal for spacecraft. Recently, metal-organic framework (MOF) derivatives have been demonstrated as high-performance catalysts for CO₂ upgrading processes. However, due to the high costs and low stability of MOF derivatives, it still remains challenge for the development of alternative synthesis methods avoiding MOF precursors. In this work, we present the sol-gel method for loading Ni-MOF to silica support in two-steps. Upon modifying the procedure, a more simplified one-step sol-gel method has been developed. Furthermore, the obtained Ni/SiO₂ catalyst still exhibits great catalytic performance with a CO₂ conversion of 77.2% and considerable CH4 selectivity of ~100% during a stability test for 52 h under a low temperature of 310 °C and high GHSV of 20,000 mL·g−1·h−1. Therefore, this work provides a ground-breaking direct strategy for loading MOF derived catalysts, and might shed a light on the preparation of highly dispersed Ni/SiO₂ catalyst.
Pastor-Pérez L., Baibars F., Le Sache E., Arellano-Garcia Harvey, Gu Sai, Ramirez Reina Tomas (2017)CO2 valorisation via Reverse Water-Gas Shift reaction using advanced Cs doped Fe-Cu/Al2O3 catalysts, In: Journal of CO2 Utilization21pp. 423-428 Elsevier
This paper evidences the viability of chemical recycling of CO2 via reverse water-gas shift reaction using advanced heterogeneous catalysts. In particular, we have developed a multicomponent Fe-Cu-Cs/Al2O3 catalyst able to reach high levels of CO2 conversions and complete selectivity to CO at various reaction conditions (temperature and space velocities). In addition, to the excellent activity, the novel-Cs doped catalyst is fairly stable for continuous operation which suggests its viability for deeper studies in the reverse water-gas shift reaction. The catalytic activity and selectivity of this new material have been carefully compared to that of Fe/Al2O3, Fe-Cu/Al2O3 and Fe-Cs/Al2O3 in order to understand each active component’s contribution to the catalyst’s performance. This comparison provides some clues to explain the superiority of the multicomponent Fe-Cu-Cs/Al2O3 catalyst
Archila Katherine, Campos Ana María, Lugo Diana Lorena, Celis Crispín Astolfo, Moreno Sonia, Ramirez Reina Tomas, Pérez-Flórez Alejandro (2020)Influence of the active phase (Fe, Ni and Ni-Fe) of mixed oxides in CWAO of Crystal Violet, In: Catalysts MDPI
The catalytic oxidation of aqueous Crystal Violet (CV) solutions has been investigated using Ni and Fe catalysts supported over Mg-Al oxides synthetized by the auto-combustion method. The influence of temperature, loading and selectivity were studied in the catalytic wet air oxidation (CWAO) of CV. The kind of metal had an important contribution in the redox process, since significant differences between Fe, Ni and their mixtures were observed. The catalysts with only Fe as active phase were more efficient for the oxidation of CV under normal conditions (T = 25 °C and atmospheric pressure) compared to those containing Ni, revealing the influence of the transition metal on catalytic properties. It was found that iron containing materials displayed enhanced textural properties. The synthesis of Fe/MgAl catalysts by the auto-combustion method, leads to solids with excellent catalytic behavior, CV degradation of 100% in eight hours of reaction, 68% of selectivity to CO2 and significant reduction of COD (Chemical oxygen demand)
Ramirez Reina Tomas, Zhang Qi, Pastor Perez Laura, Jin Wei, Gu Sai (2019)Understanding the promoter effect of Cu and Cs over highly effective -Mo2C catalysts for the reverse water-gas shift reaction, In: Applied Catalysis B: Environmental244pp. 889-898 Elsevier
Mo2C is an effective catalyst for chemical CO2 upgrading via reverse water-gas shift (RWGS). In this work, we demonstrate that the activity and selectivity of this system can be boosted by the addition of promoters such as Cu and Cs. The addition of Cu incorporates extra active sites such as Cu+ and Cu0 which are essential for the reaction. Cs is an underexplored dopant whose marked electropositive character generates electronic perturbations on the catalyst’s surface leading to enhanced catalytic performance. Also, the Cs-doped catalyst seems to be in-situ activated due to a re-carburization phenomenon which results in fairly stable catalysts for continuous operations. Overall, this work showcases a strategy to design highly efficient catalysts based on promoted β-Mo2C for CO2 recycling via RWGS.
Wang Ziling, Huang Liang, Reina Tomas Ramirez, Efstathiou Angelos M., Wang Qiang (2020)Aqueous Miscible Organic LDH Derived Ni-Based Catalysts for Efficient CO2 Methanation, In: Catalysts101168 MDPI AG
Converting CO2 to methane via catalytic routes is an effective way to control the CO2 content released in the atmosphere while producing value-added fuels and chemicals. In this study, the CO2 methanation performance of highly dispersed Ni-based catalysts derived from aqueous miscible organic layered double hydroxides (AMO-LDHs) was investigated. The activity of the catalyst was found to be largely influenced by the chemical composition of Ni metal precursor and loading. A Ni-based catalyst derived from AMO-Ni3Al1-CO3 LDH exhibited a maximum CO2 conversion of 87.9% and 100% CH4 selectivity ascribed to both the lamellar catalyst structure and the high Ni metal dispersion achieved. Moreover, due to the strong Ni metal–support interactions and abundant oxygen vacancy concentration developed, this catalyst also showed excellent resistance to carbon deposition and metal sintering. In particular, high stability was observed after 19 h in CO2/H2 reaction at 360 °C.
Ramirez Reina T, Ivanova S, Idakiev V, Delgado JJ, Ivanov I, Tabakova T, Centeno MA, Odriozola JA (2013)Impact of Ce-Fe synergism on the catalytic behaviour of Au/CeO2-FeOx/Al2O3 for pure H2 production, In: Catalysis Science and Technology3(3)pp. 779-787 The Royal Society of Chemistry
In this work the development of a series of gold catalysts, essentially based on γ-alumina promoted with a small superficial fraction of Ce–Fe mixed oxides, is reported. The catalytic behaviour is evaluated in the water gas shift reaction. The formation of a Ce–Fe solid solution is evidenced by XRD and related to the catalytic activity where the importance of the Ce–Fe interaction is demonstrated. The best catalyst reached CO conversions very close to the equilibrium limit. A long-term stability test is performed and the loss of activity is observed and attributed to reaction intermediates. Almost complete recovery of the initial conversion is achieved after oxidation treatment, suggesting that the problem of stability could be overcome by a suitable change in the reaction parameters thus leading to a highly efficient catalyst for future applications in H2 production and clean-up
Dongil Ana Belén, Guerrero-Ruiz Antonio, Zhang Qi, Pastor-Pérez Laura, Ramírez-Reina Tomás, Rodríguez-Ramos Inmaculada (2020)Effect of Cu and Cs in the β-Mo2C System for CO2 Hydrogenation to Methanol, In: Catalysts10(10)pp. 1213-1213 MDPI AG
Mitigation of anthropogenic CO2 emissions possess a major global challenge for modern societies. Herein, catalytic solutions are meant to play a key role. Among the different catalysts for CO2 conversion, Cu supported molybdenum carbide is receiving increasing attention. Hence, in the present communication, we show the activity, selectivity and stability of fresh-prepared β-Mo2C catalysts and compare the results with those of Cu/Mo2C, Cs/Mo2C and Cu/Cs/Mo2C in CO2 hydrogenation reactions. The results show that all the catalysts were active, and the main reaction product was methanol. Copper, cesium and molybdenum interaction is observed, and cesium promoted the formation of metallic Mo on the fresh catalyst. The incorporation of copper is positive and improves the activity and selectivity to methanol. Additionally, the addition of cesium favored the formation of Mo0 phase, which for the catalysts Cs/Mo2C seemed to be detrimental for the conversion and selectivity. Moreover, the catalysts promoted by copper and/or cesium underwent redox surface transformations during the reaction, these were more obvious for cesium doped catalysts, which diminished their catalytic performance.
Le Saché E., Pastor-Perez L., Watson D., Sepúlveda-Escribano A., Reina T. R. (2018)Ni stabilised on inorganic complex structures: superior catalysts for chemical CO2 recycling via dry reforming of methane, In: Applied Catalysis B: Environmental236pp. 458-465 Elsevier
CO2 utilisation is becoming an appealing topic in catalysis science due to the urgent need to deal with greenhouse gases (GHG) emissions. Herein, the dry reforming of methane (DRM) represents a viable route to convert CO2 and CH4 (two of the major GHG) into syngas, a highly valuable intermediate in chemical synthesis. Nickel-based catalysts are economically viable materials for this reaction, however they show inevitable signs of deactivation. In this work stabilisation of Ni in a pyrochlore-perovskite structure is reported as a viable method to prevent fast deactivation. Substitution of Zirconium by Ni at various loadings in the lanthanum zirconate pyrochlore La2Zr2O7 is investigated in terms of reactant conversions under various reaction conditions (temperature and space velocity). XRD analysis of the calcined and reduced catalysts showed the formation of crystalline phases corresponding to the pyrochlore structure La2Zr2-xNixO7-δ and an additional La2NiZrO6 perovskite phase at high Ni loadings. Carbon formation is limited using this formulation strategy and, as a consequence, our best catalyst shows excellent activity for DRM at temperatures as low as 600 °C and displays great stability over 350 hours of continuous operation. Exsolution of Ni from the oxide structure, leading to small and well dispersed Ni clusters, could explain the enhanced performance.
Santos J, Ramirez Reina Tomas, Ivanov I, Penkova A, Ivanova S, Tabakova T, Centeno M, Idakiev V, Odriozola J (2018)Multicomponent Au/Cu-ZnO-Al2O3 catalysts: Robust materials for clean hydrogen production, In: Applied Catalysis A: General558pp. 91-98 Elsevier
Clean hydrogen production via WGS is a key step in the development of hydrogen fuel processors. Herein, we have designed a new family of highly effective catalysts for low-temperature WGS reaction based on gold modified copper-zinc mixed oxides. Their performance was controlled by catalysts’ composition and the Au-Cu synergy. The utilization of hydrotalcite precursors leads to an optimal microstructure that ensures excellent Au and Cu dispersion and favors their strong interaction. From the application perspective these materials succeed to overcome the major drawback of the commercial WGS catalysts: resistance towards start/stop operations, a mandatory requisite for H2-powered mobile devices.
Ramirez Reina T, Ivanova S, Centeno MA, Odriozola JA (2013)Low Temperature CO oxidation on multicomponent gold based systems, In: Frontiers in Chemistry Frontiers Media
In this work the development of gold catalysts, essentially based on γ-alumina with small superficial fraction of Ce-Fe mixed oxides as support for the low temperature CO oxidation is proposed. Characterization results obtained by means of TEM, OSC, XPS, UV-Vis spectroscopy and H2-TPR are employed to correlate the activity data with the catalysts composition. The bare γ-alumina supported gold catalyst demonstrates the poorest activity within the series. The addition of CeO2 or FeOX improves the catalytic performance, especially observed for the CeO2-FeOx mixed oxide doped samples. This enhanced CO oxidation activity was related to the Ce-Fe interaction producing materials with promoted redox properties and therefore oxidation activity.
Baena-Moreno Francisco M., Rodríguez-Galán Mónica, Vega Fernando, Reina T.R., Vilches Luis F., Navarrete Benito (2019)Synergizing carbon capture storage and utilization in a biogas upgrading lab-scale plant based on calcium chloride: Influence of precipitation parameters, In: Science of The Total Environment670pp. 59-66 Elsevier
Herein a strategy for biogas upgrading in a continuous flow absorption unit using CaCl2 as capturing agent is reported. This process is presented as an alternative to the standard physical regeneration processes to capture carbon dioxide (CO2) from biogas effluents with inherent high energy penalties. This work showcases a systematic study of the main parameters (reaction time, reaction temperature, and molar ratio reactant/precipitator) affecting calcium carbonate (CaCO3) precipitation efficiency in a reaction between sodium carbonate (Na2CO3) and CaCl2. In addition, the purity and main characteristics of the obtained product were carefully analysed via in a combined characterization study using Raman, XRD, and SEM. Our results indicate that acceptable precipitation efficiencies between 62 and 93% can be reached by fine tuning the studied parameters. The characterization techniques evidence pure CaCO3 in a calcite structure. These results confirmed the technical feasibility of this alternative biogas upgrading process through CaCO3 production.
Ramirez Reina T, Ivanova S, Centeno MA, Odriozola MA (2016)The role of Au, Cu & CeO2 and their interactions for an enhanced WGS performance, In: Applied Catalysis B: Environmental187pp. 98-107 Elsevier
The WGS reaction over multicomponent Au/Ce1-xCuxO2/Al2O3 catalysts is studied in this work. The systems are carefully designed aiming to take advantage of every active phase included in the formulation: gold, ceria and copper. Special emphasis is given to the CeO2-CuO synergy and its influence on the displayed catalytic performance with and without gold. To this aim a meaningful correlation between the physicochemical properties of the mixed materials and their activity/stability is proposed. In general terms the developed catalysts present high activity under realistic WGS reaction conditions, with fairly good long term stability. In addition, the systems successfully withstand start-up/shut-downs situations, indispensable requisite for real applications in the field of pure hydrogen production for fuel cell goals
Price Cameron, Earles Emily, Pastor-Perez Laura, Liu Jian, Ramirez Reina Tomas (2018)Advantages of Yolk Shell Catalysts for the DRM: A Comparison of Ni/ZnO@SiO2 vs. Ni/CeO2 and Ni/Al2O3., In: Chemistry1(1)pp. 3-16 MDPI
Encapsulation of metal nanoparticles is a leading technique used to inhibit the main deactivation mechanisms in dry reforming of methane reaction (DRM): Carbon formation and Sintering. Ni catalysts (15%) supported on alumina (Al2O3) and ceria (CeO2) have shown they are no exception to this analysis. The alumina supported catalysts experienced graphitic carbonaceous deposits, whilst the ceria showed considerable sintering over 15 h of DRM reaction. The effect of encapsulation compared to that of the performance of uncoated catalysts for DRM reaction has been examined at different temperatures, before conducting longer stability tests. The encapsulation of Ni/ZnO cores in silica (SiO2) leads to advantageous conversion of both CO2 and CH4 at high temperatures compared to its uncoated alternatives. This work showcases the significance of the encapsulation process and its overall effects on the catalytic performance in chemical CO2 recycling via DRM.
Yu J., Odriozola J.A., Reina T. R. Dry Reforming of Ethanol and Glycerol: Mini-Review., In: Catalysts9(12)1015 MDPI AG
Dry reforming of ethanol and glycerol using CO2 are promising technologies for H2 production while mitigating CO2 emission. Current studies mainly focused on steam reforming technology, while dry reforming has been typically less studied. Nevertheless, the urgent problem of CO2 emissions directly linked to global warming has sparked a renewed interest on the catalysis community to pursue dry reforming routes. Indeed, dry reforming represents a straightforward route to utilize CO2 while producing added value products such as syngas or hydrogen. In the absence of catalysts, the direct decomposition for H2 production is less efficient. In this mini-review, ethanol and glycerol dry reforming processes have been discussed including their mechanistic aspects and strategies for catalysts successful design. The effect of support and promoters is addressed for better elucidating the catalytic mechanism of dry reforming of ethanol and glycerol. Activity and stability of state-of-the-art catalysts are comprehensively discussed in this review along with challenges and future opportunities to further develop the dry reforming routes as viable CO2 utilization alternatives.
Yang L., Pastor-Pérez L., Gu S., Sepúlveda-Escribano A., Reina T. R. (2018)Highly efficient Ni/CeO2-Al2O3 catalysts for CO2 upgrading via Reverse Water-Gas Shift: Effect of selected transition metal promoters, In: Applied Catalysis B: Environmental232pp. 464-471 Elsevier
In the context of Carbon Capture and Utilisation (CCU), the catalytic reduction of CO2 to CO via reverse water-gas shift (RWGS) reaction is a desirable route for CO2 valorisation. Herein, we have developed highly effective Ni-based catalysts for this reaction. Our study reveals that CeO2-Al2O3 is an excellent support for this process helping to achieve high degrees of CO2 conversions. Interestingly, FeOx and CrOx, which are well-known active components for the forward shift reaction, have opposite effects when used as promoters in the RWGS reaction. The use of iron remarkably boosts the activity, selectivity and stability of the Ni-based catalysts, while adding chromium results detrimental to the overall catalytic performance. In fact, the iron-doped material was tested under extreme conditions (in terms of space velocity) displaying fairly good activity/stability results. This indicates that this sort of catalysts could be potentially used to design compact RWGS reactors for flexible CO2 utilisation units.
Ramirez Reina T, Papadopoulou E, Ivanova S, Centeno T, Odriozola JA (2016)Could an excellent WGS catalyst be useful in the PROX reaction?
Ramirez Reina T, Pérez A, Ivanova S, Centeno MA, Odriozola JA (2013)H2 oxidation as a criteria for a PrOx catalyst selection
Ramirez Reina T, Ivanova S, Domínguez MI, Centeno MA, Odriozola JA (2012)Sub-ambient CO oxidation over Au/MOx/CeO2-Al2O3 (M=Zn or Fe), In: Applied Catalysis A: General419pp. 58-66
A series of ZnO and Fe2O3 modified ceria/alumina supports and their corresponding gold catalyst were prepared and studied in the CO oxidation reaction. ZnO-doped solids show a superior catalytic activity compared to the bare CeO2-Al2O3, which is attributed to the intimate contact of the ZnO and CeO2 phases, since an exchange of the lattice oxygen occurs at the interface. In a similar way, Fe2O3-modified supports increase the ability of the CeO2-Al2O3 solids to eliminate CO caused by both the existence of Ce–Fe contact surface and the Fe2O3 intrinsic activity. All of the gold catalysts were very efficient in oxidising CO irrespective of the doping metal oxide or loading, with the ZnO containing systems better than the others. The majority of the systems reached total CO conversion below room temperature with the ZnO and Fe2O3 monolayer loaded systems the most efficient within the series.
Pastor-Perez Laura, Gu Sai, Sepúlveda-Escribano Antonio, Reina Tomas R. (2019)Bimetallic Cu-Ni catalysts for the WGS reaction- Cooperative or uncooperative effect?, In: International Journal of Hydrogen Energy44(8)pp. pp 4011-4019 Elsevier
In this work, bimetallic Cu–Ni catalysts have been studied in the water-gas shift (WGS) reaction, and they have shown different levels of synergy and anti-synergy in terms of catalytic activity and selectivity to the desired products. Cu–Ni interactions alter the physicochemical properties of the prepared materials (i.e. surface chemistry, redox behaviour, etc.) and as a result, the catalytic trends are influenced by the catalysts' composition. Our study reveals that Cu enhances Ni selectivity to CO2 and H2 by preventing CO/CO2 methanation, while Ni does not help to improve Cu catalytic performance by any means. Indeed, the monometallic Cu formulation has shown the best results in this study, yielding high levels of reactants conversion and excellent long-term stability. Interestingly, for medium-high temperatures, the bimetallic 1Cu–1Ni outperforms the stability levels reached with the monometallic formulation and becomes an interesting choice even when start-up/shutdowns operations are considered during the catalytic experiments.
Yeletsky P.M., Reina T.R., Bulavchenko O.A., Saraev A.A., Gerasimov E.Yu., Zaikina O.O., Bermúdez J.M., Arcelus-Arrillaga P., Yakovlev V.A., Millan M. (2019)Phenanthrene catalytic cracking in Supercritical Water: effect of the reaction medium on NiMo/SiO2 catalysts, In: Catalysis Today329pp. 197-205 Elsevier
A series of NiMo/SiO2 catalysts was synthesized by sol-gel method for heavy oil upgrading in supercritical water (SCW). Phenanthrene was used as substrate as it represents polyaromatic structures present in asphaltenes. No phenanthrene conversion was observed in a blank (non-catalytic) experiment. However, phenanthrene conversions up to 24 % after 1 h of reaction in SCW at 425 °C and 230 bar were observed in the presence of NiMo/SiO2, underlining the role of the catalysts in the process. Conversion was found to be dependent mainly on Ni content and the Ni/Mo ratio in the catalysts. The liquid products obtained are thought to be the result of both oxidation and hydrogenation processes. Characterization of the fresh and spent catalysts using X-ray diffraction (XRD), transmission electron microscopy (TEM) and X-ray photoelectron spectroscopy (XPS) was performed. It was revealed that catalysts are not completely stable in SCW, showing that NiMo intermetallic compounds formed the initial catalysts were decomposed, Mo0 and Ni0 were oxidised and the latter formed Ni2SiO4. In addition, MoO2 phase domain size in the catalysts increased and the surface of the spent catalysts appeared to be enriched with Ni and depleted with Mo.
Sebastia-Saez Daniel, Ramirez Reina Tomas, Silva Ravi, Arellano-Garcia Harvey Synthesis and characterisation of n-octacosane@silica nano-capsules for thermal storage applications, In: International Journal of Energy Research Wiley
This work reports the synthesis and characterisation of a core-shell n-octacosane@silica nano-encapsulated phase-change material obtained via interfacial hydrolysis and poly-condensation of tetraethyl orthosilicate in mini-emulsion. Silica has been used as the encapsulating material because of its thermal advantages relative to synthesised polymers. The material presents excellent heat storage potential, with a measured latent heat varying between 57.1 and 89 kJ∙kg-1 (melting point between 58 and 64°C) and a small particle size (between ~565 and ~227 nm). Degradation of the n-octacosane core starts between 150 and 180°C. Also, the use of silica as shell material gives way to a heat conductivity of 0.796 W∙m-1∙K-1 (greater than that of nano-encapsulated materials with polymeric shell). Charge/discharge cycles have been successfully simulated at low pressure to prove the suitability of the nano-powder as phase-change material. Further investigations will be carried out in the future regarding the use of the synthesised material in thermal applications involving nanofluids.
Baena-Moreno Francisco M., Pastor-Pérez Laura, Zhang Zhien, Reina T.R. (2020)Stepping towards a low-carbon economy. Formic acid from biogas as case of study, In: Applied Energy268115033 Elsevier
The European Union has set an ambitious plan for addressing the Global Challanges in the coming years. One of these challenges is the use of biomass and the production of biomass-derived products following the spirit of a circular economy. Biogas obtained from biomass anaerobic digestion could play a pivotal role in this strategy. Herein an innovative strategy for synergizing biogas upgrading to biomethane and formic acid production from CO2 is presented. A profitability analysis of the combined biogas upgrading – CO2 utilization process was conducted to assess the economic viability of this novel approach. The profitability study focuses mainly on net present value and profitability index. Even though the process is environmentally favourable, negative profitability results are obtained. To revert the negative outputs, out of the market formic acid prices (1767–3135 €/t) would be needed to achieve a net present value equal to zero. The alternative of feed-in tariffs biomethane subsidies needs high values (121.1–269.4 €/MW) to reach profitable scenarios. These unsuccessful profitability results are ascribed to high consumables costs, mainly associated with the catalytic conversion of a CO2-rich feedstock. A 80% reduction of catalysts costs can considerably improve net present value up to 50%. This result indicates that further research is needed to find econimocally appealing catalysts to perform this process. The effect of biomethane subsidies as percentage of investment was also considered, evidencing encouraging results for small scale plants.
Ketabchi Elham, Pastor-Perez Laura, Arellano-Garcia Harvey, Reina Tomas Romarez Influence of Reaction Parameters on the Catalytic Upgrading of an Acetone, Butanol and Ethanol (ABE) Mixture: Exploring New Routes for Modern Biorefineries., In: Frontiers in Chemistry Frontiers In
Here we present a comprehensive study on the effect of reaction parameters on the upgrade of an acetone, butanol and ethanol mixture – key molecules and platform products of great interest within the chemical sector. Using a selected high performing catalyst, Fe/MgO-Al2O3, the variation of temperature, reaction time, catalytic loading and reactant molar ratio have been examined in this reaction. This work is aiming to not only optimise the reaction conditions previously used, but to step towards using less energy, time and material by testing those conditions and analysing the sufficiency of the results. Herein we demonstrate that this reaction is favored at higher temperatures and longer reaction time. Also, we observe that increasing the catalyst loading had a positive effect on the product yields, while reactant ratios have shown to produce varied results due to the role of each reactant in the complex reaction network. In line with the aim of reducing energy and costs, this work showcases that the products from the upgrading route have significantly higher market value than the reactants, highlighting this process represents an appealing route to be implemented in modern biorefineries.
Ramirez Reina T, Megias-Sayago C, Perez A, Ivanova S, Centeno MA, Odriozola JA (2015)H2 oxidation as criterion for PrOx catalyst selection: examples based on Au-CoOx supported systems, In: Journal of Catalysispp. 161-171
A new approach for understanding PrOx reaction over gold catalysts is proposed in this work. The competition between H2 and CO oxidation has been studied over a series of Au/MOx/Al2O3 (M = Ce and Co) catalysts in simulated post-reforming gas stream, containing H2O and CO2 for H2 cleanup goals. The catalysts' behavior is correlated to their oxygen storage capacity, redox behavior, and oxidation ability. The estimation of the reaction rates reveals that in these solids the H2 combustion, the selectivity limiting factor in the PrOx process, is mainly controlled by the support and not by the gold presence. The possible use of the hydrogen oxidation reaction as a catalyst selection criterion is discussed
Ramirez Reina T, Álvarez A, del Valle S, Ivanova S, Romero-Sarria F, Centeno MA, Odriozola JA (2013)Influence of the Lanthanide Oxides on the Catalytic Behavior of Au/Al2O3 Catalysts for Total and Preferential CO Oxidation, In: Advanced Chemistry Letters1(3)pp. 237-246
In this work the influence of the lanthanide series oxide addition to gold supported alumina catalyst is discussed. A clear promoting effect was observed no matter the employed reaction. Nevertheless, the presence of hydrogen in the oxidation mixture reveals interesting dissimilarities within the series of studied oxides. The differences in the catalytic behaviour of the samples are correlated to the crystal structure variations, oxygen sub-lattice disorder, gold presence and oxide's ability to undergo hydration/dehydration reactions.
Ramirez Reina T, Ivanova S, Idakiev V, Tabakova T, Centeno MA, Deng Q, Yuan Z, Odriozola JA (2016)Nanogold mesoporous iron promoted ceria catalysts for total and preferential CO oxidation reactions, In: Journal of Molecular Catalysis A: Chemical414pp. 62-71
Herein, a series of highly efficient gold based catalysts supported on mesoporous CeO2-Fe2O3 mixed oxides for CO elimination reactions have been developed. The materials have been fully characterized by means of XRD, Raman and UV-vis spectroscopies among other techniques. We identify the Ce-Fe synergism as a fundamental factor controlling the catalytic performance. Our data clearly reveal that the CO oxidation activity is maximized when the electronic and structural properties of the support are carefully controlled. In this situation, fairly good catalysts for environmental applications as for example H2 streams purification for fuel cell goals or CO abatement at room temperature can be designed
Arellano-Garcia Harvey, Ketabchi Elham, Ramirez Reina Tomas (2017)Integration of Bio-refinery Concepts in Oil Refineries, In: Proceedings of the 27th European Symposium on Computer Aided Process Engineering – ESCAPE 27pp. 829-834 Elsevier
In this work, the systematic integration of bio-refineries within oil refineries is considered. This is particularly relevant due to the lack of adaptation of existing refineries to diminishing oil supply. Moreover, the integration of oil and bio-refineries has a massively positive effect on the reduction of CO2 emissions. For instance, the biodiesel produced in bio-refineries could be integrated with conventional oil refinery processes to produce fuel, thusly reducing the dependence on crude oil. This represents a suitable alternative for increasing profit margins while being increasingly environmentally friendly. The identified possible routes of integration will be discussed in this contribution. For this purpose, the different proposed alternatives and their configurations were simulated and analysed. The developed models simulated key integrations e.g. a gasification unit that is fed from pyrolysis oil, biodiesel, and refinery residue, before being combined into one system involving all three. Varying forms of synthesis for these three feeds were also considered, focusing on novel techniques as well as environmentally friendly options that made use of waste products from other processes. The simulations revealed valuable gas stream rich in H2, with some CO2 and with a slight excess of CO resulting from the gasification unit. Further upgrading of these products was achieved by coupling the gasifier with a water gas shift (WGS) unit. This allowed a fine tune of the H2:CO ratio in the gas stream which can be further processed to obtain liquid hydrocarbons via Fischer-Tropsch (FT) synthesis or alternatively, clean hydrogen for fuel cells applications.
Le Saché Estelle, Peng Yang, Arellano-Garcia Harvey, Ramirez Reina Tomas (2017)Model-Based Analysis and Integration of Synthetic Methane Production and Methane Oxidative Coupling, In: Espuña Antonio, Graells Moisès, Puigjaner Luis (eds.), Proceedings of the 27th European Symposium on Computer Aided Process Engineering – ESCAPE 27 Elsevier
Ethylene is the world’s largest commodity chemical and a fundamental building block molecule in the chemical industry. Oxidative coupling of methane (OCM) is considered a promising route to obtain ethylene due to the potential of natural gas as a relatively economical feedstock. In a recent work, this route has been integrated by Godini et al (2013) with methane dry reforming (DRM) in a dual membrane reactor, allowing an improved thermal performance. In this work, we have explored a more ambitious integrated system by coupling the production of methane and carbon dioxide via coal gasification with the DRMOCM unit. Briefly, our process utilises coal to generate value-added methane and ethylene. In addition, CO2 management is achieved through CO2 methanation and dry methane reforming. Potential mass and energy integration between two systems is proposed as well as the optimum conditions for synthetic natural gas production. The upstream gasification process is modelled to determine the influence of temperature, pressure, and feed composition in the methane yield. The results suggest that the key variables are temperature and hydrogen concentration, as both parameters significantly affect the methane and CO2 levels in the linking stream. This study reports for the first time the linking stream between the two systems with a high methane concentration and the appropriate amount of CO2 for downstream processing.
Santos JL, Ramirez Reina T, Ivanov I, Tabakova T, Centeno MA, Idakiev V, Odriozola JA (2015)Gold modified hydrotalcite Cu/ZnO/Al2O3 catalysts for pure hydrogen production
Ramirez Reina T, Ivanova S, Centeno MA, Antonio Odriozola J (2014)Boosting the activity of Au/CeO2/Al2O3 catalysts for the WGS reaction
Ketabchi Elham, Pastor Perez Laura, Ramirez Reina Tomas, Arellano-Garcia Harvey (2020)Catalytic Upgrading of Acetone, Butanol and Ethanol (ABE): A Step Ahead for the Production of Added Value Chemicals in Bio-refineries, In: Renewable Energy156pp. 1065-1075 Elsevier
With the aim of moving towards sustainability and renewable energy sources, we have studied the production of long chain hydrocarbons from a renewable source of biomass to reduce negative impacts of greenhouse gas emissions while providing a suitable alternative for fossil fuel-based processes. Herein we report a catalytic strategy for Acetone, Butanol and Ethanol (ABE) upgrading using economically viable catalysts with potential impact in modern bio-refineries. Our catalysts based on transition metals such as Ni, Fe and Cu supported on MgO-Al2O3 have been proven to perform exceptionally with outstanding conversions towards the production of a broad range of added value chemicals from C2 to C15. Although all catalysts displayed meritorious performance, the Fe catalyst has shown the best results in terms conversion (89%). Interestingly, the Cu catalyst displays the highest selectivity towards long chain hydrocarbons (14%). Very importantly, our approach suppresses the utilization of solvents and additives resulting directly in upgraded hydrocarbons that are of use in the chemical and/ or the transportation industry. Overall, this seminal work opens the possibility to consider ABE upgrading as a viable route in bio-refineries to produce renewably sourced added value products in an economically favorable way. In addition, the described process can be envisaged as a cross-link stream among bio and traditional refineries aiming to reduce fossil fuel sources involved and incorporate “greener” solutions.
Ramirez Reina T, Ivanova S, Idakiev V, Tabakova T, Centeno MA, Odriozola JA (2012)Economically viable highly active gold based catalyst for WGSR
Price Cameron, Arnold William, Pastor-Perez Laura, Amini-Horri Bahman, Reina Thomas R. Catalytic upgrading of a biogas model mixture via low temperature DRM using multicomponent catalysts., In: Topics in Catalysis Springer Verlag
The catalytic performance of a series of bimetallic Ni-Co/CeO2-Al2O3 catalysts were evaluated within the dry reforming of methane (DRM) reaction, commonly used for upgrading biogas. The study focused on the variation of CeO2 weight loadings between 0, 10, 20 and 30%. It was found that the addition of CeO2 promoted CH4 and CO2 conversion across the temperature range and increased H2/CO ratio for the “low temperature” DRM. X-Ray Diffraction (XRD), H2-Temperature Programmed Reduction (H2-TPR) and X-Ray Photoelectron Spectroscopy (XPS) analysis revealed the formation of Ce4+ during activation of the 30% sample, resulted in excessive carbon deposition during reaction. The lowest CeO2 weight loadings exhibited softer carbon formation and limited increased chemical stability during reaction at the expense of activity. Of the tested weight loadings, 20 wt% CeO2 exhibited the best balance of catalytic activity, chemical stability and deactivation resistance in the DRM reaction. Hence this catalyst can be considered a promising system for syngas production from biogas at relatively low temperatures evidencing the pivotal role of catalysts design to develop economically viable processes for bioresources valorisation.
Ramirez Reina T, Moreno AA, Ivanova S, Ordriozola JA, Centeno MA (2012)Influence of Vanadium or Cobalt Oxides on the CO Oxidation Behavior of Au/MOx/CeO2–Al2O3 Systems, In: ChemCatChem4(4)pp. 512-520
A series of V2O5- and Co3O4-modified ceria/alumina supports and their corresponding gold catalysts were synthesized and their catalytic activities evaluated in the CO oxidation reaction. V2O5-doped solids demonstrated a poor capacity to abate CO, even lower than that of the original ceria/alumina support, owing to the formation of CeVO4. XRD, Raman spectroscopy, and H2-temperature programmed reduction studies confirmed the presence of this stoichiometric compound, in which cerium was present as Ce3+ and its redox properties were avoided. Co3O4-doped supports showed a high activity in CO oxidation at subambient temperatures. The vanadium oxide-doped gold catalysts were not efficient because of gold particle agglomeration and CeVO4 formation. However, the gold–cobalt oxide–ceria/alumina catalysts demonstrated a high capacity to abate CO at and below room temperature. Total conversion was achieved at −70 °C. The calculated apparent activation energy values revealed a theoretical optimum loading of a half-monolayer.
Reina Tomas Ramirez, Liu J., Ivanova S. Editorial: Catalysis by Gold for Gas & Liquid Phase Reactions: A Golden Future for Environmental Catalysis., In: Frontiers in Chemistry Frontiers In
This thesis presents techniques from different angles with the objective of targeting the transition towards sustainable chemical industries with minimised greenhouse gas emissions. Oil refineries are selected as a representative example of heavy carbon industries. The shutdown and decreased efficiency of oil refineries are tackled in the first section of this work through connecting that plant to a compatible one, an ethylene production plant. This presents not only enhanced operational efficiency for the oil refinery, but the ethylene production also benefits through the use of oil refinery streams that are more of use in the second plant. Through this connection, the dependency on external feed purchase was decreased leading to less dependence on crude oil, making these industries evolve in the path of sustainability. Through mass balancing and stream exchange between the two plants, a substantial profit increase is achieved for both parties using data from a typical oil refinery and ethylene plant in the UK for increased applicability. In the same line as stepping towards less fossil fuel dependence and moving towards greener solutions, an alternative for producing chemicals and/or fuel from a “green” source, biomass, is investigated with the incentive of using economically viable catalysts of Ni, Fe and Cu on MgO-Al2O3 in addition to the developing of modern bio-refineries. Using Acetone, Butanol and Ethanol as reactants which are derived from sugar fermentation, they are upgraded to long-chain organic compounds at high temperatures and pressures. Through this experimental work, outstanding conversions and selectivities were achieved compared to available research whilst also maintaining practicality since the heavy burden of expenses has been relieved. The favourability of this process is also proven through calculations showing that the amount of CO2 emissions is reduced when using this process compared to conventional fossil-fuel-based ones. This is then followed by a systematic parametric study in order to optimise the reaction conditions while also understanding the effect of each parameter on the products attained. High temperatures and catalyst loadings have proven to demonstrate the best conversions and yielding of the products. Various reactant ratios are also tested, showing the significant role of butanol in the system. This study is also conducted with the aim of saving costs, energy and material to maintain the goal of sustainability and higher profit margins when practical. Lastly, after the identification of the complex reaction network occurring, calculations via the initial rate method are carried out to determine the kinetic values of the reactions. Using this, a preliminary kinetic model using mass balancing is produced. The apparent reaction rates obtained define the slowest and fastest reactions which are successfully in line with the experimental results. These values are then used to simulate the model and optimise them for increased accuracy. Comparing the modelled and experimental values, points of strength and weakness of the model are identified, providing a novel basis for implementing this process either in industrial scales or to incorporate this into process integration with a fossil-fuel based plant stepping towards hybrid refineries. Overall, this PhD work comprises modelling and experimental approaches to pursue sustainable processes and catalytic technologies aiming to develop a low-carbon chemical industry. The underlying concepts of hybrid and bio-refineries and CO2 emissions reduction for chemicals production have been the core motivation of this work whose original contributions have resulted in several peer-reviewed publications and one patent application.