Tomas Ramirez Reina

Dr Tomas Ramirez Reina


Lecturer
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

2016-Present: 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

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.

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 Champion 

Academic Responsible of the Energy and Reaction Engineering Lab

Leader of the Catalysis Unit

Affiliations

Fellow of the Spanish Society of Catalysis, SECAT

Associate editor Frontiers in Chemistry

Editor of Chemistry - MDPI

EPSRC Peer Review College

Associate Member of the IChemE

Fellow of the Higher Education Academy 

Other activities

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

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

Panel member of the Research Foundation – Flanders (FWO

 

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”

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

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

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. 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.
  52. 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.
  53. 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
  54. 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.
  55. 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.
  56. 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.
  57. 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
  58.  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
  59. 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 Journal of membrane science – under review
  60. 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
  61. 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
  62. 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.
  63. 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
  64. 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
  65. F. Baena, M Rodriguez, F. Vega, T. 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

 

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

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. Ketanchi, 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

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, Journal of Catalysis pp. 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
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, Applied Catalysis A: General 497 pp. 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.
Centeno MA, Ramirez Reina T, Ivanova S, Laguna OH, Odriozola JA (2016) Au/CeO2 Catalysts: Structure and CO Oxidation Activity, Catalysts 6 (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.
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 Catalysis 18 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, 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, International Journal of Hydrogen Energy 40 (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.
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, Applied Catalysis B: Environmental 185 pp. 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
Ramirez Reina T, Odriozola JA, Santos JL, Ivanova S, Centeno MA, Tabakova T, Idakiev V Gold Catalysts supported in CuO/ZnO/Al2O3, production method and use of thereof,
Ramirez Reina T, Yeletski P, Bermudez J, Arcelus-Arrillaga P, Yakovlev V, Millan M (2015) Anthracene Aquacracking Using NiMo/SiO2 Catalysts in Supercritical Water Conditions, 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 E, Peng Y, Arellano-Garcia H, Ramirez Reina T (2017) Model-Based Analysis and Integration of Synthetic Methane Production and Methane Oxidative Coupling, 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.
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, Catalysis Science and Technology 3 (3) pp. 779-787 The Royal Society of Chemistry
In this work the development of a series of gold catalysts, essentially based on ³-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
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, 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, ChemCatChem 6 (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.
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?, Applied Catalysis B: Environmental 150-151 pp. 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 », 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.
Heide C, Ramirez Reina T, Millan M (2016) Phenanthrene hydrocracking using a Cr-doped NiMo/Al catalyst: Effect of the operating conditions and approach to the reaction pathway,
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, Journal of Molecular Catalysis A: Chemical 414 pp. 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
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.
R. Reina T, Xu W, Ivanova S, Centenoa MA, Hanson J, Rodriguez JA, Odriozola JA (2013) In situ characterization of iron-promoted ceria-alumina gold catalysts during the water-gas shift reaction, Catalysis Today 205 pp. 41-48 Elsevier
In this work an in situ XRD and XANES study of two gold catalysts supported on iron-promoted ceria-alumina carriers was carried out during the water-gas shift reaction (WGS). The first catalyst, Au/CeO2-FeO x/Al2O3, was prepared using a commercial alumina support in order to obtain a Ce-Fe oxide solid solution and in the second one, Au/FeOx/CeO2-Al2O3, an iron oxide monolayer was deposited onto a ceria-alumina commercial support to promote its redox properties. Catalytic activities in the WGS were remarkably different for both systems. The catalytic activity of the Au/CeO 2-FeOx/Al2O3 catalyst was higher than the one shown by the Au/FeOx/CeO2-Al 2O3 catalyst that resulted active at much higher temperatures. In situ XRD demonstrates the formation of magnetite (Fe 3O4) during the WGS reaction and the presence of big gold particles, ca. 21 nm in diameter, in the low-activity system. This in contrast to the high-activity system that shows undetectable gold nanoparticles and the absence of diffraction peaks corresponding to magnetite during the WGS. The data obtained using in situ XANES states that Ce4+ species undergo reduction to Ce3+during the WGS for both catalysts, and also confirms that in the high-activity catalyst iron is just present as Fe3+ species while in the low-activity catalyst Fe3+ and Fe2+ coexist, resulting in iron spinel observed by XRD. These results allow us conclude that the Au/CeO2-Fe2O3/Al 2O3 catalyst is a suitable catalyst for WGS when avoiding the formation of magnetite, in such a case Fe3+ species favors reduction and water splitting increasing the catalytic activity in the WGS reaction
Ramirez Reina T, Ivanova S, Centeno MA, Odriozola JA (2015) Boosting the activity of a Au/CeO2/Al2O3 catalysts for the WGS reaction, Catalysis Today 253 pp. 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.
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, Advanced Chemistry Letters 1 (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 (2015) Design and Characterization of gold based catalysts for the water gas shift reaction,
Odriozola JA, Ramirez Reina T, Centeno MA, Ivanova A, Idakiev V, Tabakova T 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 - œŸÇ/‘™2O3, 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.
Gozanlez M, Ramirez Reina T, Ivanova S, Centeno MA, Odriozola JA (2014) Pt vs. Au in water-gas shift reaction, Journal of Catalysis 314 pp. 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.
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, Proceddings of 2014 AIChE Annual Meeting 1 pp. 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.
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, ChemCatChem 4 (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.
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",
Applied Catalysis B: Environmental 197 pp. 62-72
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.
Ramirez Reina T, Ivanova S, Centeno MA, Odriozola MA (2016) The role of Au, Cu & CeO2 and their interactions for an enhanced WGS performance, Applied Catalysis B: Environmental 187 pp. 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
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, Ivanova S, Centeno MA, Odriozola JA (2013) Low Temperature CO oxidation on multicomponent gold based systems, Frontiers in Chemistry 1 (12) Frontiers Media
In this work the development of gold catalysts, essentially based on ³-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 ³-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.
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), Applied Catalysis A: General 419 pp. 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.
Ramirez Reina T, Ivanova S, Centeno M, Antonio Odriozola J (2014) Boosting the activity of Au/CeO2/Al2O3 catalysts for the WGS reaction,
Millan M, Ramirez Reina T, Bermudez JM, Puron H, Pinilla JL CATALYST FOR PROCESSING HEAVY OILS AND ITS PREPARATION METHOD,
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,
Pastor-Perez L, Ramirez Reina T, Ivanova S, Centeno MA, Odriozola JA, Sepulveda-Escribano A (2016) Ni-CeO2/C Catalysts with Enhanced OSC for the WGS Reaction, In: Feature Papers to Celebrate the Landmarks of Catalysts
Ramirez Reina T, Ivanova S, Centeno MA, Odriozola JA (2015) Viabilty of Au/CeO2-CuO/Al2O3 catalysts for pure hydrogen production via the Water-Gas Shift reaction,
Ramirez Reina T, Ivanova S, Idakiev V, Tabakova T, Centeno MA, Odriozola JA (2012) Economically viable highly active gold based catalyst for WGSR,
Volpe R, Bermúdez Menendez J, Ramirez Reina T, Messineo A, Millan M (2017) Evolution of chars during slow pyrolysis of citrus waste, Fuel Processing Technology 158 pp. 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.
Price C, Pastor-Pérez L, Le Saché E, Sepúlveda-Escribano A, Ramirez Reina T (2017) 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) 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 T, Pastor Perez L, Ivanova S, Centeno M, Odriozola J, Sepulveda-Escribano A (2015) Ni/CeO2/C catalysts with enhanced OSC for the WGS reaction, Catalysts 5 (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
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, Journal of Membrane Science 543 pp. 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.
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, Journal of CO2 Utilization 21 pp. 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
Arellano-Garcia H, Ketabchi E, Ramirez Reina T (2017) Integration of Bio-refinery Concepts in Oil Refineries, Proceedings of the 27th European Symposium on Computer Aided Process Engineering ? ESCAPE 27 pp. 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.
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,
Surface & Coatings Technology 328 pp. 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.
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.
Santos J, Ramirez Reina T, Ivanova S, Centeno M, Odriozola J (2017) Gold promoted Cu/ZnO/Al2O3 catalysts prepared from hydrotalcite precursors: Advanced materials for the WGS reaction, Applied Catalysis B: Environmental 201 pp. 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.
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, Applied Catalysis B: Environmental 224 pp. 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.
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, Catalysis Today 317 pp. 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.
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, Ceramics International 44 (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.
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-´ oxygen transport membranes under conditions relevant for oxy-fuel combustion, Journal of Membrane Science 552 pp. 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-´ (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.
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, Journal of CO2 Utilization 25 pp. 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/³-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.
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, Applied Catalysis B: Environmental 232 pp. 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.
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, Applied Catalysis A: General 558 pp. 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.
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-´ and NiFe2O4-Ce0.8Tb0.2O2-´ under real conditions for its application in oxygen transport membranes for oxyfuel combustion, Journal of Membrane Science 562 pp. 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-´ (NFO-CTO) composite and a single-phase La0.6Sr0.4Co0.2Fe0.8O3-´ (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.
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, Applied Catalysis B: Environmental 236 pp. 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-´ 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.
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, Reaction Chemistry & Engineering 3 pp. 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.
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, Journal of CO2 Utilization 27 pp. 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.
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. (2018) Phenanthrene catalytic cracking in Supercritical Water: effect of the reaction medium on NiMo/SiO2 catalysts, Catalysis Today 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.
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, Applied Catalysis B: Environmental 242 pp. 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 ( 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.
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, Processes 6 (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.
Jin Wei, Pastor- Pérez Laura, Shen DeKui, Sepúlveda-Escribano Antonio, Gu Sai, Ramirez Reina Tomas (2018) Catalytic upgrading of biomass model compounds: Novel approaches and lessons learnt from traditional hydrodeoxygenation - a review, ChemCatChem 11 (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.
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, 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.
Zhang Qi, Pastor Perez Laura, Jin Wei, Gu Sai, Ramirez Reina Tomas (2019) Understanding the promoter effect of Cu and Cs over highly effective -Mo2C catalysts for the reverse water-gas shift reaction, Applied Catalysis B: Environmental 244 pp. 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 ²-Mo2C for CO2 recycling via RWGS.
Liu Xiaoyan, Lan Guojun, Su Panpan, Qian Lihua, Ramirez Reina Tomas, Wang Liang, Li Ying, Liu Jian (2018) Highly stable Ru nanoparticles incorporated in mesoporous carbon catalysts for production of ³-valerolactone, Catalysis Today Elsevier
The hydrogenation of levulinic acid to ³-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.
Pastor-Perez Laura, Gu Sai, Sepúlveda-Escribano Antonio, Reina Tomas R. (2019) Bimetallic Cu-Ni catalysts for the WGS reaction- Cooperative or uncooperative effect?, International Journal of Hydrogen Energy 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.
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., Chemistry 1 (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.
Ramirez Reina Tomas, Pastor Perez Laura, Patel V, Le Saché Estelle (2019) CO2 methanation in the presence of methane: catalysts design and effect of methane concentration in the reaction mixture, 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.
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, International Journal of Energy Research 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.
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
Ramirez Reina Tomas, Guharoy Utsab, Olsson Emilia, Gu Sai, Cai Qiong (2019) Theoretical insights of Ni2P (0001) surface towards its potential applicability in CO2 conversion via dry reforming of methane, ACS Catalysis 9 (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.
Baena?Moreno Francisco M., Price Cameron Alexander Hurd, Le Saché Estelle, Pastor?Pérez Laura, Sebastia?Saez Daniel, Reina T. R. (2019) Physicochemical Comparison of Precipitated Calcium Carbonate for Different Configurations of a Biogas Upgrading Unit, Journal of Chemical Technology & Biotechnology 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.

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, Science of The Total Environment 670 pp. 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.
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, Energy 180 pp. 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.
Le Saché E., Pastor-Pérez L., Garcilaso V., Watson D.J., Centeno M.A., Odriozola J.A., Reina T.R. (2019) Flexible syngas production using a La2Zr2O7-´ pyrochlore-double perovskite catalyst: Towards a direct route for gas phase CO2 recycling, 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.