Tomas Ramirez Reina

Dr Tomas Ramirez Reina


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

Academic and research departments

Department of Chemical and Process Engineering.

Biography

University roles and responsibilities

  • Erasmus Coordinator
  • Faculty Mobility Leader
  • Academic Responsible of the Energy and Reaction Engineering Lab
  • Head of the Catalysis Unit
  • Member of the Teaching Committee - Year 2 Academic Rep
  • Member of the Vice-Chancellor’s Academic Consultative Ensemble (VC-ACE)
  • Co-Coordinator of the Energy and Materials Research Centre

Affiliations and memberships

HUST University China
Visiting Professor
Spanish Society of Catalysis, SECAT
Fellow
Frontiers in Chemistry
Associate Editor
Frontiers in Chemical Engineering
Associate Editor
MDPI
Editor of Chemistry
MDPI
Guess Editor of Catalysts
EPSRC
Peer Review College
IChemE
Associate Member
Higher Education Academy
Fellow
SPRINT
Board of Experts

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

Research

Research interests

Research projects

Research collaborations

Indicators of esteem

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

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

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

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

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

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

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

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

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

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

  • 11. Young Scientist award 2017 by Seville City Council.

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

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

Research grants

  • EPSRC - Global Challenges Research Fund: “Catalytic Solutions to Mitigate Global Warming in Latin America”
  • Newton-Paulet Fund Researcher Links "Sustainable Biomass Processing and Conversion"
  • Royal Society Research Grant: "Engineering Solutions for CO2 Conversion" 
  • EPSRC - CO2Chem UK seedcorn grant: “CATBIO-HYDROGEN”
  • University of Surrey RIS innovation project: "Catalytic Membranes for Green House Gases Abatement" 
  • British Council Institutional Links UK-Argentina: BIOGAS-TECH
  • EPSRC Surrey IAA: "Power to Gas using advanced catalytic membranes"
  • SPRINT - SPace Research and Innovation Network for Technology: "Micro-catalytic reactors for mono-propellant thrusters in small satellites" 
  • EPSRC Surrey IAA: "Application of Natural Materials as Catalytic and/or Support Materials for Environmentally Benign Processes"

Invited talks

  1. Tomas Ramirez Reina “Design and Characterization of gold based catalysts for the water gas shift reaction” keynote at the Spanish Conference on Catalysis, Barcelona, Spain July 2015.
  2. Tomas Ramirez Reina “Advanced oxidation reactions for sustainable energy” keynote Catalysis Doctoral Centre - University of Bath, UK, May 2017.
  3. Tomas Ramirez Reina “Design of advanced catalysts for clean hydrogen production” keynote 7th KACST-Oxford Petrochemical Forum 2017, The Royal Society, London, June 2017.
  4. Tomas Ramirez Reina “Engineering Solutions for Global Challenges” keynote INTI-University of Surrey workshop, Buenos Aires, Argentina, September 2017.
  5. Tomas Ramirez Reina “Catalysis in the context of Global Challenges” plenary lecture East China University of Science and Technology, Shanghai, China November 2017.
  6. Tomas Ramirez Reina “Advanced Catalysts for Energy and CO2 conversion applications” plenary lecture Zhengzhou University, Zhengzhou, China November 2017
  7. Tomas Ramirez Reina “Conversion of Bioresources using carbon based catalysts” keynote University of Piura, Peru June 2018.
  8. Tomas Ramirez Reina “Multicomponent catalysts for the Global Challenges” keynote Catalysis Doctoral Centre – University of Cardiff, UK, June 2018
  9. E. Le Sache, T. R. ReinaNi stabilised in La2Zr2O7: superior catalyst for gas-phase CO2 recycling” invited talk – CO2Chem UK Status Conference – awarded seedcorn grant presentation. Loughborough University, September 2018
  10. T.R.Reina “ Catalytic Systems to Address Energy Challenges” invited seminar – Research Centre for Carbon Solutions – Heriot-Watt University, Scotland November 2018.
  11. T.R.Reina  "Advanced Catalysts for a Low Carbon Future" invited Lecture - Beijing Forestry University (China), October 2019
  12. T.R. Reina "Engineering Catalysts for gas phase CO2 conversion" distinguished Webinar - Iberoamerican University, Mexico City, May 2020. 

My teaching

My publications

Publications

Transition to low carbon societies requires advanced catalysis and reaction engineering to pursue green routes for fuels and chemicals production as well as CO2 conversion. This comprehensive review provides a fresh perspective on the dry reforming of methane reaction (DRM) which constitutes a straightforward approach for effective CO2 conversion to added value syngas. The bottleneck for the implementation of this process at industrial scale is the development of highly active and robust heterogeneous catalysts able to overcome the CO2 activation barrier and deliver sufficient amount of the upgrading products at the desired operation conditions. Also, its high energy demand due to the endothermic nature of the reaction imposes extra difficulties. This review critically discusses the recent progresses on catalysts design ranging from traditional metal-supported catalysts to advanced structured and nanostructured systems with promising performance. The main advantages and culprits of the different catalytic systems are introduced aiming to inspire the catalysis community to further refine these formulations towards the development of “supercatalysts” for DRM. Besides the design of increasingly complex catalyst morphologies as well as other promising alternatives aiming at reducing the energy consumption of the process or tackle deactivation through reactor design are introduced.

Judith González-Arias, Francisco M. Baena-Moreno, Laura Pastor-Pérez, Daniel Sebastia-Saez, Luz M. Gallego Fernández, T. R. Reina (2021)Biogas upgrading to biomethane as a local source of renewable energy to power light marine transport: Profitability analysis for the county of Cornwall, In: Waste Management Elsevier

In this work, the use of biomethane produced from local biogas plants is proposed as renewable fuel for light marine transport. A profitability analysis is performed for three real biogas production plants located in Cornwall (United Kingdom), considering a total of 66 different scenarios where critical parameters such as distance from production point to gas grid, subsidies, etcetera, were evaluated. Even though the idea is promising to decarbonize the marine transport sector, under the current conditions, the approach is not profitable. The results show that profitability depends on the size of the biogas plant. The largest biogas plant studied can be profitable if feed-in tariffs subsidies between 36.6 and 45.7 €/MWh are reached, while for the smallest plant, subsidies should range between 65 and 82.7 €/MWh. The tax to be paid per ton of CO2 emitted by the shipping owner, was also examined given its impact in this green route profitability. Values seven times greater than current taxes are needed to reach profitability, revealing the lack of competitiveness of renewable fuels vs traditional fuels in this application. Subsidies to make up a percentage of the investment are also proposed, revealing that even at 100% of investment subsidized, this green approach is still not profitable. The results highlight the need for further ambitious political actions in the pursuit of sustainable societies.

Loukia-Pantzechroula Merkouri, Tomas Ramirez Reina, Melis Duyar (2021)Closing the Carbon Cycle with Dual Function Materials, In: Energy & Fuels American Chemical Society

Carbon dioxide (CO2) is one of the most harmful greenhouse gases and it is the main contributor to climate change. Its emissions have been constantly increasing over the years due to anthropogenic activities. Therefore, efforts are being made to mitigate emissions through carbon capture and storage (CCS). An alternative solution is to close the carbon cycle by utilising the carbon in CO2 as a building block for chemicals synthesis in a CO2 recycling approach that is called carbon capture and utilisation (CCU). Dual Function Materials (DFMs) are combinations of adsorbent and catalyst capable of both capturing CO2 and converting it to fuels and chemicals, in the same reactor with the help of a co-reactant. This innovative strategy has attracted attention in the past few years given its potential to lead to more efficient synthesis through the direct conversion of adsorbed CO2. DFM applications for both post combustion CCU and direct air capture (DAC) and utilisation have been demonstrated to date. In this review, we present the unique role DFMs can play in a net zero future by first providing background on types of CCU methods of varying technological maturity. Then, we present the developed applications of DFMs such as the synthesis of methane and syngas. To better guide future research efforts, we place an emphasis on the connection between DFM physiochemical properties and performance. Lastly, we discuss the challenges and opportunities of DFM development and recommend research directions for taking advantage of their unique advantages in a low-carbon circular economy.

Diana Catalina Palacio Lozano, Hugh E Jones, Tomas Ramirez Reina, Roberto Volpe, Mark P Barrow (2021)Unlocking the potential of biofuels via reaction pathways in van Krevelen diagrams, In: Green Chemistry Royal Society of Chemistry

Production of fuels and targeted chemicals from biomass represents a current challenge. Pyrolysis of biomass generates liquid bio-oils but these are highly complex mixtures. In order to obtain the desired products, optimized reaction conditions are required and this, in turn, drives the need for a fundamental understanding of the complex reaction network. Bio-oils are a complex mixture of thousands of individual molecular compositions, with differing numbers of carbon, hydrogen, nitrogen, and oxygen atoms (c, h, n, and o, respectively). The compositional spaces of such complex mixtures with high oxygen contents are commonly plotted using van Krevelen diagrams, where the H/C versus O/C ratios are displayed. For a bio-oil to be effectively used in engines, further upgrading is necessary to drive the compositions towards low oxygen and high hydrogen content (thus, low O/C and high H/C values). Here, we propose reaction vectors in van Krevelen diagrams to outline the possible reaction routes that favour the production of molecules with increased energy density, using examples of bio-oils produced from citrus waste (lemon and orange peel) and olive pulp. When reactions such as the addition or loss of CO, CO2, CH4, and H2O occur, a displacement of the compositions of molecules in terms of H/C and O/C coordinates is observed. The direction and magnitude of the displacement along each axis in van Krevelen diagrams depends upon the specific reaction route and the elemental content of each molecule. As a consequence of the wide diversity of compositions, different reaction routes are suggested that include multi-step upgrading processes, including hydrogenation and the elimination of oxygen in the form of CO and CO2. The detailed molecular composition of the starting material, plotted in van Krevelen diagrams for visualization, paves the way for greater insight into potential reaction pathways for components within these highly complex mixtures. In turn, the equations proposed hold potential to inform future production strategies, increasing the energy density of bio-oils whilst also reducing the undesirable char formation.

Laura Pastor Perez, Estelle Le Saché, C. Jones, Sai Gu, Harvey Arellano-Garcia, Tomas Ramirez Reina (2017)Synthetic natural gas production from CO 2 over Ni-x/CeO 2 -ZrO 2 (x = Fe, Co) catalysts: Influence of promoters and space velocity, In: Catalysis Today317pp. 108-113 Elsevier

Herein, the production of synthetic natural gas is proposed as an effective route for CO2 conversion. Typical catalysts for this reaction are based on Ni. In this study, we demonstrated that the addition of promoters such as iron and cobalt can greatly benefit the activity of standard Ni methanation catalysts. In particular cobalt seems to be a very efficient promoter. Our Co doped material is an outstanding catalysts for the CO2 methanation leading to high levels of CO2 conversion with selectivities close to 100%. Additionally, this catalyst is able to preserve excellent performance at relatively high space velocity which allows flexibility in the reactor design making easier the development of compact CO2 utilisation units. As an additional advantage, the Co-promoted catalysts is exceptionally stable conserving high levels of CO2 conversion under continuous operations in long terms runs.

Xiaoyan Liu, Guojun Lan, Panpan Su, Lihua Qian, Tomas Ramirez Reina, Liang Wang, Ying Li, Jian Liu (2018)Highly stable Ru nanoparticles incorporated in mesoporous carbon catalysts for production of γ-valerolactone, In: Catalysis Today Elsevier

The hydrogenation of levulinic acid to γ-valerolactone with water as solvent is a crucial reaction for producing fine chemicals. However, the development of highly stable catalysts is still a major challenge. Here, we prepared a Ru nanoparticles incorporated in mesoporous-carbon (Ru-MC) catalyst to achieve high stability in acidic aqueous medium. The Ru-MC showed excellent catalytic performance (12024h-1 turnover frequency) in the hydrogenation of LA-to3 GVL. Compared with Ru supported on mesoporous carbon catalyst (Ru/MC) prepared by conventional wet impregnation method, the Ru-MC showed excellent reusability (more than 6 times) and thermal stability (up to 600 oC). Based on H2-TPR-MS characterization, it was proposed that the incorporated structure significantly increased the interaction between Ru nanoparticles and carbon support, which effectively prevent the leaching and sintering of Ru nanoparticles and contributed to increased high reusability and thermal stability of the Ru-MC.

Wei Jin, L. Pastor- Pérez, J. Yu, J.A. Odriozola, S. Gu, T.R Reina (2019)Cost-effective routes for Catalytic Biomass Upgrading, In: Current Opinion in Green and Sustainable Chemistry

Catalytic hydrodeoxygenation (HDO) is a fundamental and promising route for bio-oil upgrading to produce petroleum-like hydrocarbon fuels or chemical building blocks. One of the main challenges of this technology is the demand of high-pressure H2, which poses high costs and safety concerns. Accordingly, developing cost-effective routes for biomass or bio-oil upgrading without the supply of commercial H2 is essential to implement the HDO at commercial scale. This paper critically reviewed the very recent studies relating to the novel strategies for upgrading the bio-feedstocks with ‘green’ H2 generated from renewable sources. More precisely, catalytic transfer hydrogenation/hydrogenolysis (CTH), combined reforming and HDO, combined metal hydrolysis and HDO, water-assisted in-situ HDO and non-thermal plasma (NTP) technology and self-supported hydrogenolysis (SSH) are reviewed herein. Current challenges and research trends of each strategy are also proposed aiming to motivate further improvement of these novel routes to become competitive alternatives to conventional HDO technology.

Wei Jin, Laura Pastor-Pérez, Juan J. Villora-Pico, Mercedes M. Pastor-Blas, Antonio Sepúlveda-Escribano, Sai Gu, Nikolaos D. Charisiou, Kyriakos Papageridis, Maria A. Goula, Tomas R. Reina (2019)Catalytic Conversion of Palm Oil to Bio-Hydrogenated Diesel over Novel N-Doped Activated Carbon Supported Pt Nanoparticles, In: Energies13(1) MDPI

Bio-hydrogenated diesel (BHD), derived from vegetable oil via hydrotreating technology, is a promising alternative transportation fuel to replace nonsustainable petroleum diesel. In this work, a novel Pt-based catalyst supported on N-doped activated carbon prepared from polypyrrole as the nitrogen source (Pt/N-AC) was developed and applied in the palm oil deoxygenation process to produce BHD in a fixed bed reactor system. High conversion rates of triglycerides (conversion of TG > 90%) and high deoxygenation percentage (DeCOx% = 76% and HDO% = 7%) were obtained for the palm oil deoxygenation over Pt/N-AC catalyst at optimised reaction conditions: T = 300 ◦C, 30 bar of H2, and LHSV = 1.5 h−1 . In addition to the excellent performance, the Pt/N-AC catalyst is highly stable in the deoxygenation reaction, as confirmed by the XRD and TEM analyses of the spent sample. The incorporation of N atoms in the carbon structure alters the electronic density of the catalyst, favouring the interaction with electrophilic groups such as carbonyls, and thus boosting the DeCOx route over the HDO pathway. Overall, this work showcases a promising route to produce added value bio-fuels from bio-compounds using advanced N-doped catalysts.

T Ramirez Reina, S Ivanova, V Idakiev, T Tabakova, MA Centeno, Q Deng, Z Yuan, JA Odriozola (2016)Nanogold mesoporous iron promoted ceria catalysts for total and preferential CO oxidation reactions, In: Journal of Molecular Catalysis A: Chemical414pp. 62-71

Herein, a series of highly efficient gold based catalysts supported on mesoporous CeO2-Fe2O3 mixed oxides for CO elimination reactions have been developed. The materials have been fully characterized by means of XRD, Raman and UV-vis spectroscopies among other techniques. We identify the Ce-Fe synergism as a fundamental factor controlling the catalytic performance. Our data clearly reveal that the CO oxidation activity is maximized when the electronic and structural properties of the support are carefully controlled. In this situation, fairly good catalysts for environmental applications as for example H2 streams purification for fuel cell goals or CO abatement at room temperature can be designed

Elham Ketabchi, Laura Pastor Perez, Tomas Ramirez Reina, Harvey Arellano-Garcia (2020)Catalytic Upgrading of Acetone, Butanol and Ethanol (ABE): A Step Ahead for the Production of Added Value Chemicals in Bio-refineries, In: Renewable Energy156pp. 1065-1075 Elsevier

With the aim of moving towards sustainability and renewable energy sources, we have studied the production of long chain hydrocarbons from a renewable source of biomass to reduce negative impacts of greenhouse gas emissions while providing a suitable alternative for fossil fuel-based processes. Herein we report a catalytic strategy for Acetone, Butanol and Ethanol (ABE) upgrading using economically viable catalysts with potential impact in modern bio-refineries. Our catalysts based on transition metals such as Ni, Fe and Cu supported on MgO-Al2O3 have been proven to perform exceptionally with outstanding conversions towards the production of a broad range of added value chemicals from C2 to C15. Although all catalysts displayed meritorious performance, the Fe catalyst has shown the best results in terms conversion (89%). Interestingly, the Cu catalyst displays the highest selectivity towards long chain hydrocarbons (14%). Very importantly, our approach suppresses the utilization of solvents and additives resulting directly in upgraded hydrocarbons that are of use in the chemical and/ or the transportation industry. Overall, this seminal work opens the possibility to consider ABE upgrading as a viable route in bio-refineries to produce renewably sourced added value products in an economically favorable way. In addition, the described process can be envisaged as a cross-link stream among bio and traditional refineries aiming to reduce fossil fuel sources involved and incorporate “greener” solutions.

T Ramirez Reina, S Ivanova, MA Centeno, MA Odriozola (2016)The role of Au, Cu & CeO2 and their interactions for an enhanced WGS performance, In: Applied Catalysis B: Environmental187pp. 98-107 Elsevier

The WGS reaction over multicomponent Au/Ce1-xCuxO2/Al2O3 catalysts is studied in this work. The systems are carefully designed aiming to take advantage of every active phase included in the formulation: gold, ceria and copper. Special emphasis is given to the CeO2-CuO synergy and its influence on the displayed catalytic performance with and without gold. To this aim a meaningful correlation between the physicochemical properties of the mixed materials and their activity/stability is proposed. In general terms the developed catalysts present high activity under realistic WGS reaction conditions, with fairly good long term stability. In addition, the systems successfully withstand start-up/shut-downs situations, indispensable requisite for real applications in the field of pure hydrogen production for fuel cell goals

Estelle Le Saché, Yang Peng, Harvey Arellano-Garcia, Tomas Ramirez Reina (2017)Model-Based Analysis and Integration of Synthetic Methane Production and Methane Oxidative Coupling, In: 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.

T. Stroud, Tristan Smith, Estelle Le Saché, J.L. Santos, M.A. Centeno, Harvey Arellano-Garcia, J.A. Odriozola, Tomas Ramirez Reina (2017)Chemical CO2 recycling via dry and bi reforming of methane using Ni-Sn/Al2O3 and Ni-Sn/CeO2-Al2O3 catalysts, In: Applied Catalysis B: Environmental224pp. 125-135 Elsevier

Carbon formation and sintering remain the main culprits regarding catalyst deactivation in the dry and bi-reforming of methane reactions (DRM and BRM, respectively). Nickel based catalysts (10 wt.%) supported on alumina (Al2O3) have shown no exception in this study, but can be improved by the addition of tin and ceria. The effect of two different Sn loadings on this base have been examined for the DRM reaction over 20 h, before selecting the most appropriate Sn/Ni ratio and promoting the alumina base with 20 wt.% of CeO2. This catalyst then underwent activity measurements over a range of temperatures and space velocities, before undergoing experimentation in BRM. It not only showed good levels of conversions for DRM, but exhibited stable conversions towards BRM, reaching an equilibrium H2/CO product ratio in the process. In fact, this work reveals how multicomponent Ni catalysts can be effectively utilised to produce flexible syngas streams from CO2/CH4 mixtures as an efficient route for CO2 utilisation.

JL Santos, T Ramirez Reina, I Ivanov, T Tabakova, MA Centeno, V Idakiev, JA Odriozola (2015)Gold modified hydrotalcite Cu/ZnO/Al2O3 catalysts for pure hydrogen production
T Ramirez Reina, S Ivanova, MA Centeno, J Antonio Odriozola (2014)Boosting the activity of Au/CeO2/Al2O3 catalysts for the WGS reaction
T Ramirez Reina, A Pérez, S Ivanova, MA Centeno, JA Odriozola (2013)H2 oxidation as a criteria for a PrOx catalyst selection
W. Jin, L. Pastor-Perez, Juan J. Villora-Picó, A. Sepúlveda-Escribano, S. Gu, T. R. Reina (2019)Investigating New Routes for Biomass Upgrading: “H2-Free” Hydrodeoxygenation Using Ni-Based Catalysts, In: ACS Sustainable Chemistry & Engineering7(19)pp. 16041-16049 American Chemical Society

This work showcases an innovative route for biocompound upgrading via hydrodeoxygenation (HDO) reactions, eliminating the need for external high-pressure hydrogen supply. We propose the use of water as reaction media and the utilization of multifunctional catalysts that are able to conduct multiple steps such as water activation and HDO. In this study, we validate our hypothesis in a high-pressure batch reactor process using guaiacol as a model compound and multicomponent Ni-based catalysts. In particular, a comparison between ceria-supported and carbon/ceria-supported samples is established, the carbon-based materials being the suitable choice for this reaction. The physicochemical study by X-ray photoelectron spectroscopy, transmission electron microscopy, X-ray diffraction, and temperature-programmed reduction reveals the greater dispersion of Ni clusters and the strong metal-support interaction in the carbon/ceria-based samples accounting for the enhanced performance. In addition, the characterization of the spent samples points out the resistance of our catalysts toward sintering and coking. Overall, the novel catalytic approach proposed in this paper opens new research possibilities to achieve low-cost bio-oil upgrading processes.

T Ramirez Reina, S Ivanova, V Idakiev, T Tabakova, MA Centeno, JA Odriozola (2012)Economically viable highly active gold based catalyst for WGSR
T Ramirez Reina, E Papadopoulou, S Ivanova, T Centeno, JA Odriozola (2016)Could an excellent WGS catalyst be useful in the PROX reaction?
Laura Pastor-Perez, Sai Gu, Antonio Sepúlveda-Escribano, Tomas R. Reina (2019)Bimetallic Cu-Ni catalysts for the WGS reaction- Cooperative or uncooperative effect?, In: International Journal of Hydrogen Energy44(8)pp. pp 4011-4019 Elsevier

In this work, bimetallic Cu–Ni catalysts have been studied in the water-gas shift (WGS) reaction, and they have shown different levels of synergy and anti-synergy in terms of catalytic activity and selectivity to the desired products. Cu–Ni interactions alter the physicochemical properties of the prepared materials (i.e. surface chemistry, redox behaviour, etc.) and as a result, the catalytic trends are influenced by the catalysts' composition. Our study reveals that Cu enhances Ni selectivity to CO2 and H2 by preventing CO/CO2 methanation, while Ni does not help to improve Cu catalytic performance by any means. Indeed, the monometallic Cu formulation has shown the best results in this study, yielding high levels of reactants conversion and excellent long-term stability. Interestingly, for medium-high temperatures, the bimetallic 1Cu–1Ni outperforms the stability levels reached with the monometallic formulation and becomes an interesting choice even when start-up/shutdowns operations are considered during the catalytic experiments.

Harvey Arellano-Garcia, Elham Ketabchi, Tomas Ramirez Reina (2017)Integration of Bio-refinery Concepts in Oil Refineries, In: Proceedings of the 27th European Symposium on Computer Aided Process Engineering – ESCAPE 27pp. 829-834 Elsevier

In this work, the systematic integration of bio-refineries within oil refineries is considered. This is particularly relevant due to the lack of adaptation of existing refineries to diminishing oil supply. Moreover, the integration of oil and bio-refineries has a massively positive effect on the reduction of CO2 emissions. For instance, the biodiesel produced in bio-refineries could be integrated with conventional oil refinery processes to produce fuel, thusly reducing the dependence on crude oil. This represents a suitable alternative for increasing profit margins while being increasingly environmentally friendly. The identified possible routes of integration will be discussed in this contribution. For this purpose, the different proposed alternatives and their configurations were simulated and analysed. The developed models simulated key integrations e.g. a gasification unit that is fed from pyrolysis oil, biodiesel, and refinery residue, before being combined into one system involving all three. Varying forms of synthesis for these three feeds were also considered, focusing on novel techniques as well as environmentally friendly options that made use of waste products from other processes. The simulations revealed valuable gas stream rich in H2, with some CO2 and with a slight excess of CO resulting from the gasification unit. Further upgrading of these products was achieved by coupling the gasifier with a water gas shift (WGS) unit. This allowed a fine tune of the H2:CO ratio in the gas stream which can be further processed to obtain liquid hydrocarbons via Fischer-Tropsch (FT) synthesis or alternatively, clean hydrogen for fuel cells applications.

Wei Jin, Jose Luis Santos, Laura Pastor-Perez, Sai Gu, Miguel Angel Centeno, Tomas Ramirez Reina (2019)Noble metal supported on activated carbon for "hydrogen free" HDO reactions: exploring economically advantageous routes for biomass valorisation, In: ChemCatChem Wiley

An innovative route for bio‐compounds upgrading via “hydrogen‐free” hydrodeoxygenation (HDO) is proposed and evaluated using guaiacol as a model compound in a high‐pressure batch reactor. Experimental results showed that noble metal supported on activated carbon catalysts are able to conduct tandem multiple steps including water splitting and subsequent HDO. The activity of Ru/C catalyst is superior to other studied catalysts (i.e. Au/C, Pd/C and Rh/C) in our water‐only HDO reaction system. The greater dispersion and smaller metal particle size confirmed by the TEM micrographs accounts for the better performance of Ru/C. This material also presents excellent levels of stability as demonstrated in multiple reciclabylity runs. Overall, the proposed novel approach confirmed the viability of oxygenated bio‐compounds upgrading in a water‐only reaction system suppressing the need of external H2 supply and can be rendered as a fundamental finding for the economical biomass valorisation to produce added value bio‐fuels.

Katherine Archila, Ana María Campos, Lorena Lugo, Crispín Astolfo Celis, Sonia Moreno, Tomas Ramirez Reina, Alejandro Pérez-Flórez (2020)Influence of the Active Phase (Fe, Ni, and Ni–Fe) of Mixed Oxides in CWAO of Crystal Violet, In: Catalysts10(9) MDPI

The catalytic oxidation of aqueous crystal violet (CV) solutions was investigated using Ni and Fe catalysts supported over Mg–Al oxides synthesized by the autocombustion method. The influence of temperature, loading, and selectivity were studied in the catalytic wet air oxidation (CWAO) of CV. The kind of metal had an important contribution in the redox process as significant differences were observed between Fe, Ni, and their mixtures. The catalysts with only Fe as active phase were more efficient for the oxidation of CV under normal conditions (T = 25 °C and atmospheric pressure) compared to those containing Ni, revealing the influence of the transition metal on catalytic properties. It was found that iron-containing materials displayed enhanced textural properties. The synthesis of Fe/MgAl catalysts by the autocombustion method led to solids with excellent catalytic behavior, 100% CV degradation in eight hours of reaction, 68% selectivity to CO₂, and significant reduction of chemical oxygen demand (COD).

Tomas Ramirez Reina, Laura Pastor Perez, S Ivanova, MA Centeno, JA Odriozola, A Sepulveda-Escribano (2015)Ni/CeO2/C catalysts with enhanced OSC for the WGS reaction, In: Catalysts5(1)pp. 298-309 MDPI AG

In this work, the WGS performance of a conventional Ni/CeO2 bulk catalyst is compared to that of a carbon-supported Ni-CeO2 catalyst. The carbon-supported sample resulted to be much more active than the bulk one. The higher activity of the Ni-CeO2/C catalyst is associated to its oxygen storage capacity, a parameter that strongly influences the WGS behavior. The stability of the carbon-supported catalyst under realistic operation conditions is also a subject of this paper. In summary, our study represents an approach towards a new generation of Ni-ceria based catalyst for the pure hydrogen production via WGS. The dispersion of ceria nanoparticles on an activated carbon support drives to improved catalytic skills with a considerable reduction of the amount of ceria in the catalyst formulation

Utsab Guharoy, Tomas Ramirez Reina, Sai Gu, Qiong Cai (2019)Mechanistic Insights into Selective CO2 Conversion via RWGS on Transition Metal Phosphides: A DFT Study, In: Journal of Physical Chemistry C123(37)pp. 22918-22931 American Chemical Society

Selective conversion of CO2 to CO via the reverse water gas shift (RWGS) reaction is an attractive CO2 conversion process, which may be integrated with many industrial catalytic processes such as Fischer−Tropsch synthesis to generate added value products. The development of active and cost friendly catalysts is of paramount importance. Among the available catalyst materials, transition metal phosphides (TMPs) such as MoP and Ni2P have remained unexplored in the context of the RWGS reaction. In the present work, we have employed density functional theory (DFT) to first investigate the stability and geometries of selected RWGS intermediates on the MoP (0001) surface, in comparison to the Ni2P (0001) surface. Higher adsorption energies and Bader charges are observed on MoP (0001), indicating better stability of intermediates on the MoP (0001) surface. Furthermore, mechanistic investigation using potential energy surface (PES) profiles showcased that both MoP and Ni2P were active toward RWGS reaction with the direct path (CO2* → CO* + O*) favorable on MoP (0001), whereas the COOH-mediated path (CO2* + H* → COOH*) favors Ni2P (0001) for product (CO and H2O) gas generation. Additionally, PES profiles of initial steps to CO activation revealed that direct CO decomposition to C* and O* is favored only on MoP (0001), while H-assisted CO activation is more favorable on Ni2P (0001) but could also occur on MoP (0001). Furthermore, our DFT calculations also ascertained the possibility of methane formation on Ni2P (0001) during the RWGS process, while MoP (0001) remained more selective toward CO generation.

Cameron Alexander Hurd Price, Laura Pastor-Perez, Tomas Ramirez Reina, Jian Liu (2020)Yolk-Shell structured NiCo@SiO₂ nanoreactor for CO₂ upgrading via reverse water-gas shift reaction, In: Catalysis Today Elsevier

This work reports the successful and simplistic synthesis of highly uniform NiCo@SiO₂ yolk@shell catalysts, with their effectiveness towards CO₂ recycling investigated within the RWGS reaction. The engineered microstructure catalysts display high CO₂ conversion levels and a remarkable selectivity for CO as main reaction product across the whole examined temperatures. Interestingly, the selectivity is affected by Ni loading reflecting a close correlation catalytic performance/material structure-composition. Further to this behaviour, the designed nanoreactor exhibits considerable deactivation resistance and performance under reaction cycling conditions and appears to demonstrate the production of larger organic molecules after qualitative analysis of the product gas by mass spectrometry. These results demonstrate the effectiveness of the spatial confinement effect, imbued to the material from its advanced morphology, through its influence of deactivation resistance and control of reactive selectivity.

MA Centeno, T Ramirez Reina, S Ivanova, OH Laguna, JA Odriozola (2016)Au/CeO2 Catalysts: Structure and CO Oxidation Activity, In: Catalysts6(10)158 MDPI AG

In this comprehensive review, the main aspects of using Au/CeO2 catalysts in oxidation reactions are considered. The influence of the preparation methods and synthetic parameters, as well as the characteristics of the ceria support (presence of doping cations, oxygen vacancies concentration, surface area, redox properties, etc.) in the dispersion and chemical state of gold are revised. The proposed review provides a detailed analysis of the literature data concerning the state of the art and the applications of gold–ceria systems in oxidation reactions.

S Pirou, J Bermudez, B Tak Na, J Yu, P Vang Hendriksen, A Kaiser, Tomas Ramirez Reina, M Millan, R Kiebach (2018)Performance and stability of (ZrO2)0.89(Y2O3)0.01(Sc2O3)0.10-LaCr0.85Cu0.10Ni0.05O3-δ oxygen transport membranes under conditions relevant for oxy-fuel combustion, In: Journal of Membrane Science552pp. 115-123 Elsevier

Self-standing, planar dual-phase oxygen transport membranes consisting of 70 vol.% (ZrO2)0.89(Y2O3)0.01(Sc2O3)0.10 (10Sc1YSZ) and 30 vol.% LaCr0.85Cu0.10Ni0.05O3-δ (LCCN) were successfully developed and tested. The stability of the composite membrane was studied in simulated oxy-fuel power plant flue-gas conditions (CO2, SO2, H2O). The analyses of the exposed composites by X-ray diffraction (XRD), X-ray fluorescence (XRF), attenuated total reflection Fourier transform infrared spectroscopy (ATR-FTIR) and Raman spectroscopy revealed an excellent stability. Oxygen permeation fluxes were measured across 1000 µm thick and 110 µm thick self-supported 10Sc1YSZ-LCCN (70-30 vol.%) membranes from 700 °C to 950 °C using air as the feed gas and N2 or CO2 as the sweep gas. The 110 µm thick membrane, prepared by tape-casting and lamination processes, showed oxygen fluxes up to 1.02 mLN cm-2 min-1 (950 °C, air/N2). Both membranes demonstrated stable performances over long-term stability tests (250-300 h) performed at 850 °C using pure CO2 as the sweep gas.

JA Odriozola, T Ramirez Reina, M Gonzalez-Castano, S Ivanova, MA Centeno (2014)Unrevealing the mechanism of the WGS reaction over Au/CeO2-FeOx/Al2O3 catalysts, In: Proceddings of 2014 AIChE Annual Meeting1pp. 498-499

Hydrogen-alimented fuel cells (FC) have a strong potential to play a decisive role in the new energy system for the coming years. The production of H2 pure enough to use it in fuel cells requires the development of very efficient catalysts for the WGS reaction. In our group several gold-ceria based catalysts have been developed presenting very promising results in this process [1,2]. The successful catalytic design makes mandatory an accurate knowledge about the reaction mechanism and the active species involved in the process. In order to address these issues a combination of several in-situ/operando characterization techniques is performed in this work using an optimized Au/CeO2-FeOx/Al2O3 catalyst. Synchrotron-based in-situ time-resolved Xray absorption spectroscopy (TR-XAS) and operando DRIFTS during the WGS reaction are employed with the ultimate goal to establish structure-activity relations and to propose the most likely reaction pathways.

Cristina Megías-Sayago, Tomas Ramirez Reina, Svetlana Ivanova, Jose A. Odriozola (2019)Au/CeO2-ZnO/Al2O3 as Versatile Catalysts for Oxidation Reactions: Application in Gas/Liquid Environmental Processes, In: Frontiers in Chemistry7504pp. 1-10 Frontiers Media

The present work showcases the versatility of nanogold systems supported on Zn-doped ceria when applied in two important environmental processes, the total CO oxidation, and the liquid phase oxidation of glucose to gluconic acid. In the CO oxidation the suitability of these materials is clearly demonstrated achieving full conversions even at sub-ambient conditions. Regarding the glucose oxidation our materials display high conversion values (always over 50%) and very importantly full or almost full selectivity toward gluconic acid—an added value platform chemical in the context of biomass upgrading routes. The key factors controlling the successful performance on both reactions are carefully discussed and compared to previous studies in literature. To our knowledge this is one of the very few works in catalysis by gold combining liquid and gas phase reactions and represents a step forward in the flexible behavior of nano gold catalysts.

J Bermudez, J Garcia-Fayos, Tomas Ramirez Reina, G Reed, E Persoon, D Görtz, M Schroeder, M Millan, J Serra (2018)Thermochemical stability of LaxSr1-xCoyFe1-yO3-δ and NiFe2O4-Ce0.8Tb0.2O2-δ under real conditions for its application in oxygen transport membranes for oxyfuel combustion, In: Journal of Membrane Science562pp. 26-37 Elsevier

This work addresses the thermochemical stability of ceramic materials –typically used in oxygen transport membranes– under the harsh gas environments found in oxyfuel combustion processes. Specifically, a dual-phase NiFe2O4-Ce0.8Tb0.2O2-δ (NFO-CTO) composite and a single-phase La0.6Sr0.4Co0.2Fe0.8O3-δ (LSCF) were studied. The effect of the main contaminants present in this kind of processes (CO2, SO2 and H2O) has been tested. NFO-CTO composite remains stable under all the conditions studied whereas LSCF presents a poor stability in the presence of CO2 and SO2. Regardless of the treatment, NFO-CTO conserves its crystalline structure, without giving rise to new species due to segregation or incorporation of sulphur and/or carbon. On the contrary, LSCF is prone to degradation in contact with CO2 and SO2, segregating Sr in the form of SrCO3 and SrSO4 and Co and Fe in the form of CoO and Fe3O4. It is also shown that SO2 interaction with LSCF is stronger than in the case of CO2. A concentration of just 2000 ppm of SO2 in CO2 is enough to subdue the formation of SrCO3, promoting the segregation of Sr only in the form of SrSO4. With the results presented in this work, it is possible to conclude that the NFO-CTO is a suitable candidate from the thermochemical viewpoint to be used as membrane material in 4-end modules for oxygen generation integrated into oxyfuel combustion processes whereas the use of LSCF should be dismissed.

Cameron Alexander Hurd Price, William Arnold, Laura Pastor-Perez, Bahman Amini-Horri, Tomas Ramirez Reina (2019)Catalytic upgrading of a biogas model mixture via low temperature DRM using multicomponent catalysts, In: Topics in Catalysis Springer Verlag

The catalytic performance of a series of bimetallic Ni-Co/CeO2-Al2O3 catalysts were evaluated within the dry reforming of methane (DRM) reaction, commonly used for upgrading biogas. The study focused on the variation of CeO2 weight loadings between 0, 10, 20 and 30%. It was found that the addition of CeO2 promoted CH4 and CO2 conversion across the temperature range and increased H2/CO ratio for the “low temperature” DRM. X-Ray Diffraction (XRD), H2-Temperature Programmed Reduction (H2-TPR) and X-Ray Photoelectron Spectroscopy (XPS) analysis revealed the formation of Ce4+ during activation of the 30% sample, resulted in excessive carbon deposition during reaction. The lowest CeO2 weight loadings exhibited softer carbon formation and limited increased chemical stability during reaction at the expense of activity. Of the tested weight loadings, 20 wt% CeO2 exhibited the best balance of catalytic activity, chemical stability and deactivation resistance in the DRM reaction. Hence this catalyst can be considered a promising system for syngas production from biogas at relatively low temperatures evidencing the pivotal role of catalysts design to develop economically viable processes for bioresources valorisation.

S Pirou, JM Bermudez, P Vang Hendriksen, A Kaiser, Tomas Ramirez Reina, M Millan, R Kiebach (2017)Stability and performance of robust dual-phase (ZrO2)0.89(Y2O3)0.01(Sc2O3)0.10-Al0.02Zn0.98O1.01 oxygen transport membranes, In: Journal of Membrane Science543pp. 18-27 Elsevier

Dual-phase composite oxygen transport membranes consisting of 50 vol% Al0.02Zn0.98O1.01 and 50 vol% (ZrO2)0.89(Y2O3)0.01(Sc2O3)0.10 were successfully developed and tested. The applicability of the membrane in oxy-fuel power plants schemes involving direct exposure to flue gas was evaluated by exposing the membrane to gas streams containing CO2, SO2, H2O and investigating possible reactions between the membrane material and these gases. The analyses of the exposed composites by x-ray diffraction (XRD), x-ray fluorescence (XRF), attenuated total reflection Fourier transform infrared spectroscopy (ATR-FTIR), and Raman spectroscopy revealed excellent stability. Additionally, an electrical conductivity measurement over 900 h confirmed that the composite is stable under prolonged exposure to CO2. However, an instability of the dual-phase membrane under oxygen partial pressures below PO2~10−4 atm. was found. Oxygen permeation tests on a 1 mm thick self-standing membrane resulted in an oxygen flux of 0.33 mLN min−1 cm−2 at 925 °C in air/N2. Stability tests in CO2 with 3 vol% O2 demonstrated the potential for the use of 10Sc1YSZ-AZO dual-phase membranes in oxy-combustion processes involving direct exposure to flue gas.

T Ramirez Reina, P Yeletsky, JM Bermudez, P Arcelus-Arrillaga, V Yakovlev, M Millan (2016)Anthracene aquacracking using NiMo/SiO2 catalysts in supercritical water conditions, In: Fuel: the science and technology of fuel and energy182pp. 740-748

A series of effective NiMo/SiO2 catalysts for heavy oil upgrading in supercritical water have been developed. Experimental results with anthracene as model compound resembling structures present in heavy oils showed that the catalytic activity as well as the liquid and gas product distributions are governed by catalyst composition. In particular by adjusting the Ni/Mo ratio different physicochemical properties (crystalline phase composition, particle size and catalysts reducibility) are obtained, which have influence on catalytic behavior. A variety of liquid products together with a valuable gas (rich in H2) are produced in this process, which takes place with remarkably low coke deposition on the catalysts. Overall, the results derived from this work confirm the viability of upgrading polyaromatic structures in supercritical water using Ni-Mo catalysts and provides an insight on the main parameters to control in catalyst design.

T Ramirez Reina, JA Odriozola, JL Santos, S Ivanova, MA Centeno, T Tabakova, V Idakiev (2016)Gold Catalysts supported in CuO/ZnO/Al2O3, production method and use of thereof
Francisco M. Baena-Moreno, Fernando Vega, Laura Pastor-Pérez, T.R. Reina, Benito Navarrete, Zhien Zhang (2019)Novel Process for Carbon Capture and Utilization and Saline Wastes Valorization, In: Journal of Natural Gas Science and Engineering103071 Elsevier

Herein a novel process for CO₂ capture and utilization suitable for small-medium scale applications is presented. The use of potassium and calcium wastes is proposed as an alternative low-energy path to CO₂ capture and waste valorization. In our work, CaCO₃ precipitation studies were performed to corroborate the feasibility of the novel process described. Reaction time, reaction temperature, molar ratio, and K₂CO₃ initial concentration were varied to analyse their effects on the precipitation efficiency. The purity and main characteristics of the obtained product were physicochemically characterized to evaluate the potential cost of the final solid product by means of Raman spectroscopy, X-ray diffraction, FTIR, and scanning electron microscopy. Results show that promising precipitation efficiencies are obtained in comparison with other waste-valorization and CO₂ capture process, even at room temperatures. High quality calcite was obtained as solid product. Overall our work confirms the technical viability of the proposed route to synergize CO₂ capture and saline waste utilization.

O transport membranes (OTM) are a promising alternative to conventional systems of air separation based on cryogenic distillation for oxy-fuel combustion power plants. In this work, a systematic study of the thermochemical stability of La0.6Sr0.4Co0.2 Fe0.8O3 (perovskite-type) and cobalt doped Ce0.9Gd0.1O (fluorite-type) is proposed. The experiments were developed in a laboratory scale facility, which is able to mimic realistic oxy-fuel combustion flue gas containing SOx, NOx, H2O and CO2. In order to understand the thermochemical behavior of this type of materials, a full characterization analysis of the tested samples using a wide portfolio of analytical techniques such as X-ray diffraction (XRD), X-ray fluorescence (XRF), infrared spectroscopy (ATR-FTIR), Raman spectroscopy, scanning electron microscopy with energy-dispersive X-ray spectroscopy (SEM-EDS) and Brunauer−Emmett−Teller analysis (BET) has been carefully discussed. Our data revealed the superior stability of the CGO samples in comparison with the LSCF at all the test conditions studied in this work. The formation of crystalline and amorphous sulphates and carbonates are evident for the LSCF while for the CGO samples do not react with SOX and barely form carbonates. The presence of silicon species – typically ignored in academic works – has been detected, pointing its relevance for real applications.

Laura Pastor-Perez, Mihir Shah, Estelle Le Saché, Tomas Ramirez Reina (2018)Improving Fe/Al2O3 catalysts for the Reverse Water-Gas Shift reaction: on the effect of Cs as activity/selectivity promoter, In: Catalysts MDPI

Abstract: The conversion of CO2 into CO via the Reverse Water-Gas Shift (RWGS) reaction is a suitable route for CO2 valorisation. Fe-based catalysts are highly active for this reaction but their activity and selectivity can be substantially boosted by adding Cs as a promoter. In this work we demonstrate that Cs modifies the redox behaviour and the surface chemistry of the iron based materials. The metallic dispersion and the amount of metallic Fe centres available for the reaction depends on Cs loading. 5 wt.% of Cs is an optimum amount of dopant to achieve a fair activity/selective balance. Nevertheless, depending on the RWGS reactor operational temperature, lower concentrations of Cs also lead to acceptable catalytic performance. Along with the excellent activity of the prepared materials this work showcases their robustness for long-term runs and the strong impact of H2/CO ratio in the overall catalytic performance.

T Ramirez Reina, S Ivanova, OH Laguna, MA Centeno, JA Odriozola (2016)WGS and CO-PrOx reactions using gold promoted copper-ceria catalysts: “Bulk CuO CeO2 vs. CuO CeO2/Al2O3 with low mixed oxide content”, In: Applied Catalysis B: Environmental1697pp. 62-7

A copper-ceria bulk catalyst has been compared to a series of catalysts designed according to the as called “supported approach”, corresponding to the dispersion of low content mixed copper-ceria oxide on alumina matrix. The principal characteristics of both types of catalysts are contemplated and the differences in their electronic and redox properties discussed in details. As a plus, the gold metal promotion of the catalysts is also envisaged. The advantages of the systems in the CO clean up reactions, WGS and CO-PrOx are commented. While the WGS activity appears to be ruled especially by the Cu/Ce surface to volume ratio, the CO-PrOx reaction is governed by the CuO loading. Gold addition provides benefits only at the low temperature WGS regime. Very importantly, the supported systems are always superior to the bulk configuration in terms of specific activity, a key factor from the catalyst’s design perspective.

C-A Hurd Price, L Pastor-Pérez, Tomas Ramirez Reina, Jian Liu (2018)Robust mesoporous bimetallic yolk-shell catalysts for chemical CO2 upgrading via dry reforming of methane, In: Reaction Chemistry & Engineering3pp. 433-436 Royal Society of Chemistry

Here, we report the synthesis of mesoporous ZnO/Ni@m-SiO2 yolk-shell particles. The unique ZnO/Ni@m-SiO2 catalysts demonstrate impressive resistance to sintering and coking for dry reforming of methane (DRM). They also display long term stability with high levels of conversion and selectivity, making this catalyst promising for chemical CO2 upgrading.

P Boldrin, E Ruiz-Trejo, J Mermelstein, J Bermudez Menendez, T Ramirez Reina, NP Brandon (2016)Strategies for carbon and sulfur tolerant solid oxide fuel cell materials, incorporating lessons from heterogeneous catalysis, In: Chemical Reviews

Solid oxide fuel cells (SOFCs) are a rapidly emerging energy technology for a low carbon world, providing high efficiency, potential to use carbonaceous fuels and compatibility with carbon capture and storage. However, current state-of-the-art materials have low tolerance to sulfur, a common contaminant of many fuels, and are vulnerable to deactivation due to carbon deposition when using carbon-containing compounds. In this review we first study the theoretical basis behind carbon and sulfur poisoning, before examining the strategies towards carbon and sulfur tolerance used so far in the SOFC literature. We then study the more extensive relevant heterogeneous catalysis literature for strategies and materials which could be incorporated into carbon and sulfur tolerant fuel cells.

Mohammadmehdi Choolaei, Tomas Ramirez Reina, Bahman Amini Horri (2020)Synthesis and characterisation of nanocrystalline CuO–Fe2O3/GDC anode powders for solid oxide fuel cells, In: Ceramics International Elsevier

This paper deals with the development and potential application of a novel mixed ionic-electronic conductive anode composite comprised of copper and iron oxide based on gadolinium-doped ceria (CuO–Fe2O3/GDC) for solid-oxide fuel cell (SOFC). Synthesis of the nanocrystalline CuO–Fe2O3/GDC powders was carried out using a novel co-precipitation method based on ammonium tartrate as the precipitant in a mixed-cationic solution composed of Cu2+, Fe3+, Gd3+, and Ce3+. Thermal decomposition of the resultant precipitate after drying (at 55 °C) was investigated in a wide range of temperature (25–900 °C) using simultaneous DSC/TGA technique in air. The DSC/TGA results suggested the optimal calcination temperature of 500 °C for obtaining the nanocrystalline anode composite from the resultant precipitate. The synthesised CuO–Fe2O3/GDC samples were further characterised using XRD, dilatometry, FESEM, and EDX. Several single cells of SOFCs were fabricated in the anode-supported geometry using the synthesised CuO–Fe2O3/GDC composite as the anode, GDC/CuO composite as the electrolyte, and LSCF/GDC composite as the cathode layer. The fabricated cells were analysed using FESEM imaging and EIS analysis, where an equivalent circuit containing five R-CPE terms was used to interpret the EIS data. The module fitted well the impedance data and allowed for a detailed deconvolution of the total impedance spectra. The catalytic activity and uniformity of the synthesised nanocomposites was further evaluated using TPR analysis, demonstrating excellent activity at temperatures as low as 200 °C.

Cameron Price, L Pastor-Pérez, Estelle Le Saché, A Sepúlveda-Escribano, Tomas Ramirez Reina (2017)Highly active Cu-ZnO catalysts for the WGS reaction at medium-high space velocities: effect of the support composition, In: International Journal of Hydrogen Energy42(16)pp. 10747-10751 Elsevier

Cu-ZnO based catalysts are the benchmark materials for the low-temperature WGS reaction. However, they present a crucial drawback which limits their application in portable devices: they only work under very low space velocities. In this study, we have developed a series of multicomponent Cu-ZnO catalysts able to work at relatively high space velocities with outstanding activity and stability. Different reference supports have been utilised with CeO2-Al2O3 being the most promising system. Overall, this work describes a strategy to design advanced Cu-based catalysts that can overcome the residence time restrictions in the WGS reaction.

Wei Jin, Laura Pastor- Pérez, DeKui Shen, Antonio Sepúlveda-Escribano, Sai Gu, Tomas Ramirez Reina (2018)Catalytic upgrading of biomass model compounds: Novel approaches and lessons learnt from traditional hydrodeoxygenation - a review, In: ChemCatChem11(3)pp. 924-960 Wiley

Catalytic hydrodeoxygenation (HDO) is a fundamental process for bio-resources upgrading to produce transportation fuels or added value chemicals. The bottleneck of this technology to be implemented at commercial scale is its dependence on high pressure hydrogen, an expensive resource which utilization also poses safety concerns. In this scenario, the development of hydrogen-free alternatives to facilitate oxygen removal in biomass derived compounds is a major challenge for catalysis science but at the same time it could revolutionize biomass processing technologies. In this review we have analyzed several novel approaches, including catalytic transfer hydrogenation (CTH), combined reforming and hydrodeoxygenation, metal hydrolysis and subsequent hydrodeoxygenation along with non-thermal plasma (NTP) in order to avoid the supply of external H2. The knowledge accumulated from traditional HDO sets the grounds for catalysts and processes development among the hydrogen alternatives. In this sense, mechanistic aspects for HDO and the proposed alternatives are carefully analyzed in this work. Biomass model compounds are selected aiming to provide an indepth description of the different processes and stablish solid correlations catalysts composition-catalytic performance which can be further extrapolated to more complex biomass feedstocks. Moreover, the current challenges and research trends of novel hydrodeoxygenation strategies are also presented aiming to spark inspiration among the broad community of scientists working towards a low carbon society where bio-resources will play a major role.

T Ramirez Reina, S Ivanova, JJ Delgado, I Ivanov, T Tabakova, V Idakiev, MA Centeno, JA Odriozola (2014)Viabilty of Au/CeO2-ZnO/Al2O3 catalysts for pure hydrogen production by the Water-Gas Shift reaction, In: ChemCatChem6(5)pp. 1401-1401

The production of H2 pure enough for use in fuel cells requires the development of very efficient catalysts for the water–gas shift reaction. Herein, a series of gold catalysts supported on ZnO-promoted CeO2–Al2O3 are presented as interesting systems for the purification of H2 streams through the water–gas shift reaction. The addition of ZnO remarkably promotes the activity of an Au/CeO2/Al2O3 catalyst. This increase in activity is mainly associated with the enhanced oxygen storage capacity exhibited for the Zn-containing solids. High activity and good stability and resistance towards start-up–shut-down situations was found, which makes these catalysts a promising alternative for CO clean-up applications.

The development of catalytic materials for the recycling CO2 through a myriad of available processes is an attractive field, especially given the current climate change. While there is increasing publication in this field, the reported catalysts rarely deviate from the traditionally supported metal nanoparticle morphology, with the most simplistic method of enhancement being the addition of more metals to an already complex composition. Encapsulated catalysts, especially yolk@shell catalysts with hollow voids, offer answers to the most prominent issues faced by this field, coking and sintering, and further potential for more advanced phenomena, for example, the confinement effect, to promote selectivity or offer greater protection against coking and sintering. This work serves to demonstrate the current position of catalyst development in the fields of thermal CO2 reforming and hydrogenation, summarizing the most recent work available and most common metals used for these reactions, and how yolk@shell catalysts can offer superior performance and survivability in thermal CO2 reforming and hydrogenation to the more traditional structure. Furthermore, this work will briefly demonstrate the bespoke nature and highly variable yolk@shell structure. Moreover, this review aims to illuminate the spatial confinement effect and how it enhances yolk@shell structured nanoreactors is presented.

M Gozanlez, T Ramirez Reina, S Ivanova, MA Centeno, JA Odriozola (2014)Pt vs. Au in water-gas shift reaction, In: Journal of Catalysis314pp. 1-1

This work presents a comparison of the gold- and platinum-based catalysts behavior in the water-gas shift (WGS) reaction. The influence of the support, e.g., its composition and electronic properties, studied in detail by means of UV-Vis spectroscopy, of the metal nature and dispersion and of the stream composition has been evaluated. The catalytic performance of the samples is directly correlated with the electronic properties modification as a function of metal and/or support. Both metals present high activity in the selected reaction although in a different operation temperature window.

T Ramirez Reina, M González Castaño, S Palma, S Ivanova (2014)Twenty Years of Golden Future in the Water Gas Shift Reaction, In: Heterogeneous Gold Catalysts and Catalysis18(5)pp. 111-139 Royal Society of Chemistry

Once considered an inert element, gold has recently gained attention as a catalyst. This book presents a comprehensive review of this rapidly-evolving field. It provides readers with a thorough background to the use of gold in catalysis, as well as the latest methods for the preparation of gold catalysts. Written to be accessible by postgraduates and newcomers to the field, this book is also beneficial to experienced researchers and is an essential reference in the laboratory.

Francisco M. Baena‐Moreno, Cameron Alexander Hurd Price, Estelle Le Saché, Laura Pastor‐Pérez, Daniel Sebastia Saez, T. R. Reina (2019)Physicochemical Comparison of Precipitated Calcium Carbonate for Different Configurations of a Biogas Upgrading Unit, In: Journal of Chemical Technology & Biotechnology94(7)pp. 2256-2262 Wiley

BACKGROUND This paper presents a physicochemical comparison of the solid products obtained from two alternative processes that recycle waste sodium carbonate (Na2CO3) solution, which is produced following the absorption of CO2 in a biogas‐upgrading unit. Chemical regeneration processes offer an attractive alternative to the energetically demanding standard physical methods. In the first process, sodium hydroxide (NaOH) is regenerated as a precipitate from the chemical reaction of Na2CO3 with calcium hydroxide (Ca(OH)2). The second process shows a path to obtain a valuable sodium chloride (NaCl) and Calcium carbonate (CaCO3) rich brine from calcium chloride (CaCl2) acting as a precipitant agent. In both processes, Precipitated Calcium Carbonate (PCC) is obtained as the most valuable by‐product, but with varying properties due to the different origin. RESULTS The purpose of this work is to analyse physicochemically both variations of PCCs obtained and examining the differences between these solid samples in order to determine which method produces more desirable characteristics in the final product. To this end, FTIR, Raman, XRD and SEM were employed as characterization methods. The results reflect that both PCCs have a calcite crystal structure, or morph, being as both PCC products originate from CaCl2 that is more similar to commercial calcium carbonate calcite. CONCLUSION These results confirmed that a pure CaCO3 valuable by‐product can be obtained from a biogas upgrading unit with several industrial applications.

T Ramirez Reina, JL Santos, N García-Moncada, S Ivanova, JA Odriozola (2016)Development of Robust Mixed-Conducting Membranes with High Permeability and Stability, In: 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.

Qi Zhang, L. Pastor-Perez, S. Gu, Tomas Ramirez Reina (2020)Transition Metal Carbides (TMCs) catalysts for gas phase CO2 upgrading reactions: a comprehensive overview, In: Catalysts MDPI

Increasing demand for CO2 utilization reactions and the stable character of CO2 have motivated the interest in developing highly active, selective and stable catalysts. Precious metal catalysts have been studied extensively due to their high activities, but their implementation for industrial applications is hindered due to their elevated cost. Among the materials which have comparatively low prices, transition metal carbides (TMCs) are deemed to display catalytic properties similar to Pt-group metals (Ru, Rh, Pd, Ir, Pt) in several reactions such as hydrogenation and dehydrogenation processes. In addition, they are excellent substrates to disperse metallic particles. Hence, the unique properties of TMCs make them ideal substitutes for precious metals resulting in promising catalysts for CO2 utilization reactions. This work aims to provide a comprehensive overview of recent advances on TMCs catalysts towards gas phase CO2 utilization processes, such as CO2 methanation, reverse water gas shift (rWGS) and dry reforming of methane (DRM). We have carefully analyzed synthesis procedures, performances and limitations of different TMCs catalysts. Insights on material characteristics such as crystal structure and surface chemistry and their connection with the catalytic activity are also critically reviewed.

R Volpe, JM Bermúdez Menendez, Tomas Ramirez Reina, A Messineo, M Millan (2017)Evolution of chars during slow pyrolysis of citrus waste, In: Fuel Processing Technology158pp. 255-263 Elsevier

Conversion of agro-wastes into energy can be key to a circular-driven economy that could lead tomodels for sustainable production. Thermochemical processing is an interesting alternative for the upgrading of agro-wastes to energy. However, owing to the complex and largely unknown set of reactions occurring during thermal breakdown, to ensuring consistent quality of the final products is still a goal to achieve at industrial level. The present study investigates the evolution of solid products of pyrolysis, to gain some insights in these complexities. Chars derived fromslowpyrolysis (200–650 °C) of citrus pulp in a horizontal reactor have been characterized bymeans of Fourier Transform Infrared spectroscopy (FT-IR), X-Ray Diffraction (XRD), ThermoGravimetric Analysis (TGA) and Scanning Electron Microscopy (SEM). Results are discussed also in light of similarities with coal thermal breakdown. At temperatures below 300 °C, changes in solid matrix are mainly due to breaking of aliphatic compounds. Significant changes in char structure and behavior then occur between 300 °C and 500 °C mainly related to secondary char-tar reactions. Above 500 °C, changes appear to occur mainly due to recombination reactions within matrix, which thereby becomes progressively less reactive.

T Ramirez Reina, S Ivanova, MA Centeno, JA Odriozola (2015)Catalytic screening of Au/CeO2-MOx/Al2O3 catalysts (M= La,Ni,Cu,Fe,Cr,Y) in the CO-PrOx reaction, In: International Journal of Hydrogen Energy40(4)pp. 1782-1788

In this work, a series of Au/CeO2-MOx/Al2O3 catalysts has been prepared and evaluated in the PrOx reaction. Within the series of dopants Fe and Cu containing samples enhanced the catalytic performance of the parent Au/CeO2/Al2O3 catalyst being copper the most efficient promoter. For both samples an enhanced oxygen storage capacity (OSC) is registered and accounts for the high CO oxidation activity. More particularly, the Au/CeO2-CuOx/Al2O3 catalyst successfully withstands the inclusion of water in the PrOx stream and presents good results in terms of CO elimination. However to achieve a good selectivity toward CO2 formation properly adjusting of the reaction parameters, such as oxygen concentration and space velocity is needed. Within the whole screened series the Cu-containing catalyst can be considered as the most interesting alternative for H2 clean-up applications.

Francisco M. Baena-Moreno, Laura Pastor-Pérez, Qiang Wang, T.R. Reina (2020)Bio-methane and bio-methanol co-production from biogas: A profitability analysis to explore new sustainable chemical processes, In: Journal of Cleaner Production265121909 Elsevier

Herein a potential synergy between biogas upgrading and CO2 conversion to bio-methanol is investigated. This novel idea arises as an alternative path to the traditional biogas – to – bio-methane route which involves CO2 separation. In this work a techno-economic analysis of the process was performed to study the profitability for potential investors. A total of 15 scenarios were analysed. Different biogas plant sizes were examined as baseline scenarios: 100, 250, 500, and 1000 m³/h. Furthermore the potential effect of governmental incentives through bio-methane subsidies (feed-in tariffs and investment percentage) was studied. Finally a sensitivity analysis was developed to study the effect of key parameters. The results of the baseline scenarios demonstrated that not profitable results can be obtained without subsidies. Bio-methane subsidies as feed-in tariffs proved to be effective for the 500 and 1000 m³/h plant sizes. For a feed-in tariff subsidy of 40 €/MW, 500 m³/h biogas production plants are remarkably profitable (net present value equal to 3106 k€). Concerning 1000 m³/h biogas production plants, 20 €/MW of subsidies as feed-in tariffs gives similar net present value result. Our results point out that only big biogas production can produce bio-methanol at profitable margins under 90–100% of investment subsidied. The sensitivity analysis showed that electricity, natural gas and bio-methanol price can affect considerably to the overall profitability, converting predicted positive cases in negative scenarios.

Francisco M. Baena-Moreno, Mónica Rodríguez-Galán, Fernando Vega, T. R. Reina, Luis F. Vilches, Benito Navarrete (2019)Converting CO2 from biogas and MgCl2 residues into valuable magnesium carbonate: A novel strategy for renewable energy production, In: Energy180pp. 457-464 Elsevier

In this work a novel strategy for bio-methane production and magnesium chloride waste valorization is addressed. The proposed process is a potential alternative path to the already existing biogas upgrading technologies by carbon dioxide mineralization into valuable magnesium carbonate. The main parameters affecting the precipitation efficiency (reaction time, reaction temperature, and molar ratio reactant/precipitator) are studied, leading to promising results which spark further investigation in this innovative route. Additionally the purity and the morphology of the obtained solid product was accurately analysed through different physicochemical characterization techniques such as Raman, X-Ray diffraction and Scanning electron microscope. The characterisation study reveals a mixture of Nesqueonite and Dypingite carbonate phases obtained in the process being the later the dominant phase in the resulting precipitate. Overall, the results discussed herein confirmed the technical feasibility of this innovative strategy for synergizing carbon dioxide mineralization and renewable energy production.

T Ramirez Reina, S Ivanova, MA Centeno, JA Odriozola (2015)Boosting the activity of a Au/CeO2/Al2O3 catalysts for the WGS reaction, In: Catalysis Today253pp. 149-154

Herein a strategy to design highly efficient Au/CeO2/Al2O3 based WGS catalysts is proposed. The inclusion of transition metals, namely Fe, Cu and Zn as CeO2 dopant is considered. All the promoters successfully increased the WGS performance of the undoped sample. The activity improvement can be correlated to structural and/or redox features induced by the dopants. The comparative characterization of the doped samples by means of XRD, Raman spectroscopy and OSC evaluation permits an accurate understanding of the boosted WGS activity arising from the Ce-promoter interaction. This study establishes distinction among both, structural and redox sources of promotion and provides a useful strategy to develop highly active Au/CeO2 based catalysts for the WGS reaction.

Tomas Ramirez Reina, Francisco Manuel Baena Moreno (2020)Profitability analysis of a novel configuration to synergize Biogas Upgrading and Power-to-Gas", In: Energy Conversion and Management Elsevier
M Gonzalez-Castano, T Ramirez Reina, S Ivanova, M Martinez-Tejada, MA Centeno, JA Odriozola (2016)O2-assisted Water Gas Shift reaction using Au and Pt structured catalysts, In: Applied Catalysis B: Environmental185pp. 337-343 Elsevier

Platinum and gold structured catalysts were compared as active phases in classical and O2-assisted Water Gas Shift (WGS) reaction. Both metals were supported on iron-doped ceria mixed oxide and then, structured on metallic micromonolithic devices. As expected the WGS activity of both micromonoliths is conditioned by the nature of the noble metals being Pt the most active metal in traditional conditions. However, the addition of oxygen to the classical water gas feed turns the balance in favor of the gold based catalysts, being the presence of gold responsible for an excessive improvement of the catalytic activity

Utsab Guharoy, Estelle Le Saché, Qiong Cai, Tomas Ramirez Reina, Sai Gu (2018)Understanding the role of Ni-Sn interaction to design highly effective CO2 conversion catalysts for dry reforming of methane, In: Journal of CO2 Utilization27pp. 1-10 Elsevier

CO2 reforming of methane is an effective route for carbon dioxide recycling to valuable syngas. However conventional catalysts based on Ni fail to overcome the stability requisites in terms of resistance to coking and sintering. In this scenario, the use of Sn as promoter of Ni leads to more powerful bimetallic catalysts with enhanced stability which could result in a viable implementation of the reforming technology at commercial scale. This paper uses a combined computational (DFT) and experimental approach, to address the fundamental aspects of mitigation of coke formation on the catalyst’s surface during dry reforming of methane (DRM). The DFT calculation provides fundamental insights into the DRM mechanism over the mono and bimetallic periodic model surfaces. Such information is then used to guide the design of real powder catalysts. The behaviour of the real catalysts mirrors the trends predicted by DFT. Overall the bimetallic catalysts are superior to the monometallic one in terms of long-term stability and carbon tolerance. In particular, low Sn concentration on Ni surface effectively mitigate carbon formation without compromising the CO2 conversion and the syngas production thus leading to excellent DRM catalysts. The bimetallic systems also presents higher selectivity towards syngas as reflected by both DFT and experimental data. However, Sn loading has to be carefully optimized since a relatively high amount of Sn can severely deter the catalytic performance.

JL Santos, Tomas Ramirez Reina, S Ivanova, MA Centeno, JA Odriozola (2017)Gold promoted Cu/ZnO/Al2O3 catalysts prepared from hydrotalcite precursors: Advanced materials for the WGS reaction, In: Applied Catalysis B: Environmental201pp. 310-317

Outstanding catalysts for the water was shift reaction are reported in this work. The combination of gold nanoparticles with Cu/ZnO/Al2O3 prepared from hydrotalcite-like precursors leads to very promising systems for pure hydrogen production. Full CO conversion is reached at temperatures as low as 180 °C. The key point seems to be the cooperation of Au and Cu and the optimal metal-oxide contact derived from the synthesis method. The high activity of gold for low temperature CO oxidation and the suitability of copper for the WGS results in a perfect synergy. Moreover the materials developed in this work present good stability and tolerance towards start/stop cycles an indispensable requisite for a realistic application in an integrated hydrogen fuel processor.

O Arbelaez, T Ramirez Reina, S Ivanova, F Bustamente, AL Villa, MA Centeno, JA Odriozola (2015)Mono and bimetallic Cu-Ni structured catalysts for the water gas shift reaction, In: Applied Catalysis A: General497pp. 1-9

The water-gas shift (WGS) reaction over structured Cu, Ni, and bimetallic Cu-Ni supported on active carbon (AC) catalysts was investigated. The structured catalysts were prepared in pellets form and applied in the medium range WGS reaction. A good activity in the 180–350 °C temperature range was registered being the bimetallic Cu-Ni:2-1/AC catalyst the best catalyst. The presence of Cu mitigates the methanation activity of Ni favoring the shift process. In addition the active carbon gasification reaction was not observed for the Cu-containing catalyst converting the active carbon in a very convenient support for the WGS reaction. The stability of the bimetallic Cu-Ni:2-1/AC catalyst under continuous operation conditions, as well as its tolerance towards start/stop cycles was also evaluated.

I Unal, S Meisuria, Mohammadmehdi Choolaei, Tomas Ramirez Reina, Bahman Amini Horri (2018)Synthesis and Characteristics of Nanocrystalline Ni1-xCoxO/GDC Powder as a Methane Reforming Catalyst for SOFCs, In: Ceramics International44(6)pp. 6851-6860 Elsevier

This paper has described the application of nickel-doped catalytic constituents based on gadolinium-doped ceria (GDC) for fabrication of the solid-oxide fuel cell (SOFC) anode layer integrated with an in-situ methane-reforming layer (MRL). Nanocrystalline powders of Ni1-xCo3xO1+3x/GDC and Ni1-xCuxO/GDC with various compositions (x = 0.3, 0.5, 0.7) were synthesised using an ultrasound-assisted method followed by a thermal treatment to be applied for fabrication of the integrated MRL and the SOFC anode layer, respectively. Thermogravimetric analysis showed that the synthesized powders should be optimally calcined at 700 °C to exhibit improved crystallinity and catalytic activity. The morphological analysis showed the formation of nanocrystalline powders with particle size ranging from 4-86 nm that was confirmed by the crystal size analysis using XRD results. The elemental analysis by EDX indicated a successful distribution of the constituent ceramic and bimetallic phases after the addition of a sonication stage. The results of FT-IR and Raman spectroscopy confirmed lack of solvents residual after calcination that was in agreement with residual moisture content values obtained from TGA data. The fabricated anode-MRL bilayers had an adequate porosity (36.7%) and shrinkage (33.5%) after adding carbon particles as a pore former (at a loading fraction of 5.9 wt.%). The catalytic performance measurements of the MRL showed a methane conversion of 13% at maximum activity with a weight hour space velocity (WHSV) of 60 L/gh that was mainly due to carbon deposition in the reaction condition.

Cameron Alexander Hurd Price, Tomas Ramirez Reina, Jian Liu (2020)Engineering heterogenous catalysts for chemical CO₂ utilization: Lessons from thermal catalysis and advantages of yolk@shell structured nanoreactors, In: Journal of Energy Chemistry Elsevier

The development of catalytic materials for the recycling CO₂ through a myriad of available processes is an attractive field, especially given the current climate change. While there is increasing publication in this field, the reported catalysts rarely deviate from the traditionally supported metal nanoparticle morphology, with the most simplistic method of enhancement being the addition of more metals to an already complex composition. Encapsulated catalysts, especially yolk@shell catalysts with hollow voids, offer answers to the most prominent issues faced by this field, coking and sintering, and further potential for more advanced phenomena, for example, the confinement effect, to promote selectivity or offer greater protection against coking and sintering. This work serves to demonstrate the current position of catalyst development in the fields of thermal CO₂ reforming and hydrogenation, summarizing the most recent work available and most common metals used for these reactions, and how yolk@shell catalysts can offer superior performance and survivability in thermal CO₂ reforming and hydrogenation to the more traditional structure. Furthermore, this work will briefly demonstrate the bespoke nature and highly variable yolk@shell structure. Moreover, this review aims to illuminate the spatial confinement effect and how it enhances yolk@shell structured nanoreactors is presented.

F.M Baena-Moreno, N Cid-Castillo, H Arellano-García, T.R Reina (2021)Towards emission free steel manufacturing – Exploring the advantages of a CO2 methanation unit to minimize CO2 emissions, In: The Science of the total environment781146776 Elsevier B.V

This paper demonstrates the benefits of incorporating CO2 utilisation through methanation in the steel industry. This approach allows to produce synthetic methane, which can be recycled back into the steel manufacturing process as fuel and hence saving the consumption of natural gas. To this end, we propose a combined steel-making and CO2 utilisation prototype whose key units (shaft furnace, reformer and methanation unit) have been modelled in Aspen Plus V8.8. Particularly, the results showed an optimal performance of the shaft furnace at 800 °C and 6 bar, as well as 1050 °C and atmospheric pressure for the reformer unit. Optimal results for the methanation reactor were observed at 350 °C. Under these optimal conditions, 97.8% of the total CO2 emissions could be mitigated from a simplified steel manufacturing scenario and 89.4% of the natural gas used in the process could be saved. A light economic approach is also presented, revealing that the process could be profitable with future technologic developments, natural gas prices and forthcoming increases of CO2 emissions taxes. Indeed, the cash-flow can be profitable (325 k€) under the future costs: methanation operational cost at 0.105 €/Nm3; electrolysis operational cost at 0.04 €kWh, natural gas price at 32 €/MWh; and CO2 penalty at 55€/MWh. Hence this strategy is not only environmentally advantageous but also economically appealing and could represent an interesting route to contribute towards steel-making decarbonisation. [Display omitted] •Engineering solutions to curb CO2 emissions in steel-making processes•Advantages of a methanation unit for a greener steel production•Profitability analysis of a CO2 conversion•Optimisation of key parameters to showcase the benefits of the methanation process

Liuqingqing Yang, Laura Pastor Perez, J.J Villora-Pico, Sai Gu, A. Sepúlveda-Escribano, Tomas Ramirez Reina (2020)CO2 valorisation via Reverse Water-Gas Shift reaction using promoted Fe/CeO2-Al2O3 catalysts: showcasing the potential of advanced catalysts to explore new processes design, In: APPLIED CATALYSIS A-GENERAL593117442 ELSEVIER SCIENCE BV

The RWGS reaction represents a direct approach for gas-phase CO2 upgrading. This work showcases the efficiency of Fe/CeO2-Al2O3 catalysts for this process, and the effect of selected transition metal promoters such as Cu, Ni and Mo. Our results demonstrated that both Ni and Cu remarkably improved the performance of the monometallic Fe-catalyst. The competition Reverse Water-Gas Shift (RWGS) reaction/CO2 methanation reaction was evident particularly for the Ni-catalyst, which displayed high selectivity to methane in the low-temperature range. Among the studied catalysts the Cu promoted sample represented the best choice, exhibiting the best activity/selectivity balance. In addition, the Cu-doped catalyst was very stable for long-term runs – an essential requisite for its implementation in flue gas upgrading units. This material can effectively catalyse the RWGS reaction at medium-low temperatures, providing the possibility to couple the RWGS reactor with a syngas conversion reaction. Such an integrated unit opens the horizons for a direct CO2 to fuels/chemicals approach.

Katherine Archila, Ana María Campos, Diana Lorena Lugo, Crispín Astolfo Celis, Sonia Moreno, Tomas Ramirez Reina, Alejandro Pérez-Flórez (2020)Influence of the active phase (Fe, Ni and Ni-Fe) of mixed oxides in CWAO of Crystal Violet, In: Catalysts MDPI

The catalytic oxidation of aqueous Crystal Violet (CV) solutions has been investigated using Ni and Fe catalysts supported over Mg-Al oxides synthetized by the auto-combustion method. The influence of temperature, loading and selectivity were studied in the catalytic wet air oxidation (CWAO) of CV. The kind of metal had an important contribution in the redox process, since significant differences between Fe, Ni and their mixtures were observed. The catalysts with only Fe as active phase were more efficient for the oxidation of CV under normal conditions (T = 25 °C and atmospheric pressure) compared to those containing Ni, revealing the influence of the transition metal on catalytic properties. It was found that iron containing materials displayed enhanced textural properties. The synthesis of Fe/MgAl catalysts by the auto-combustion method, leads to solids with excellent catalytic behavior, CV degradation of 100% in eight hours of reaction, 68% of selectivity to CO2 and significant reduction of COD (Chemical oxygen demand)

Aderlanio Cardoso, Tomas Ramirez Reina, Isabel Suelves, José Luis Pinilla, Marcos Millan, Klaus Hellgardt (2018)Effect of carbon-based materials and CeO2 on Ni catalysts for Kraft lignin liquefaction in supercritical water, In: Green chemistry : an international journal and green chemistry resource : GC20(18)pp. 4308-4318 Royal Society of Chemistry

Kraft lignin (KL) is a by-product from cellulose production typically treated as a waste or used as a low-value fuel in heat and power generation in the pulp and paper industry. This study explores KL upgrading to monoaromatic compounds using supercritical water (SCW) as reaction medium. The effect of Ni–CeO2 catalysts supported on carbon nanofibers (CNF) and activated carbon (AC) on the product distribution was investigated. These catalysts were prepared by a wet-impregnation method with acetone, and reduced Ni was observed without the use of H2. CNF presented a high degree of stability in SCW. Ni in its reduced state was still present in all spent catalysts, mainly when CNF were the support. While catalysts supported in AC led to high yields of char and gas, a 56 wt% yield of a light liquid fraction, recovered as dichloromethane (DCM)-soluble product and consisting mainly of (methoxy)phenols (>80 mol%), was obtained in a batch reactor at 400 °C, 230 bar, with Ni–CeO2/CNF as a catalyst. A short reaction time was key to avoid the formation of gas and char. This study demonstrates that high yields of DCM-soluble products from KL and low char formation can be obtained by using only SCW and catalysts, an alternative to widely reported approaches like the addition of organic co-solvents (e.g., phenol) and/or H2.

Tomas Ramirez Reina, (2021)Analysis of the potential for biogas upgrading to syngas via catalytic reforming in the United Kingdom, In: Renewable and Sustainable Energy Reviews Elsevier

The UK faces unprecedented environmental challenges which require urgent action. The promotion of renewable energy sources is a promising solution to tackle these challenges. Among the renewable options, syngas production from biogas via dry reforming of methane shows great potential as a green alternative to meet global environmental goals. The purpose of this work is to estimate the potential of syngas production from biogas in the UK and its profitability. To estimate the syngas production, we present an overview of methane dry reforming to syngas. This analysis reveals that nickel/alumina catalysts are the most popular choice for the mentioned reaction. Afterwards, the potential biogas production in the UK is obtained. Both set of data are subsequently combined to estimate the potential for syngas production from biomass in the UK. A techno-economic analysis is performed to estimate the syngas price to reach profitability. This analysis reveals syngas prices ranging from 1.154 to 1.564 €/m3 to overcome production costs, which is higher than producing syngas from traditional fossil fuels. Further analysis has also been conducted to estimate the production of different utilisation routes for said syngas including biofuel, methanol and electricity.

Ana Belén Dongil, Qi Zhang, Laura Pastor-Pérez, Tomás Ramírez-Reina, Antonio Guerrero-Ruiz, Inmaculada Rodríguez-Ramos (2020)Effect of Cu and Cs in the β-Mo2C System for CO2 Hydrogenation to Methanol, In: Catalysts10(10)pp. 1213-1213 MDPI AG

Mitigation of anthropogenic CO2 emissions possess a major global challenge for modern societies. Herein, catalytic solutions are meant to play a key role. Among the different catalysts for CO2 conversion, Cu supported molybdenum carbide is receiving increasing attention. Hence, in the present communication, we show the activity, selectivity and stability of fresh-prepared β-Mo2C catalysts and compare the results with those of Cu/Mo2C, Cs/Mo2C and Cu/Cs/Mo2C in CO2 hydrogenation reactions. The results show that all the catalysts were active, and the main reaction product was methanol. Copper, cesium and molybdenum interaction is observed, and cesium promoted the formation of metallic Mo on the fresh catalyst. The incorporation of copper is positive and improves the activity and selectivity to methanol. Additionally, the addition of cesium favored the formation of Mo0 phase, which for the catalysts Cs/Mo2C seemed to be detrimental for the conversion and selectivity. Moreover, the catalysts promoted by copper and/or cesium underwent redox surface transformations during the reaction, these were more obvious for cesium doped catalysts, which diminished their catalytic performance.

Francisco M Baena-Moreno, Miriam Gonzalez-Castaño, Harvey Arellano-García, TOMAS RAMIREZ REINA (2021)Exploring profitability of bioeconomy paths: Dimethyl ether from biogas as case study, In: Energy (Oxford)225120230 Elsevier Ltd

Herein a novel path is analysed for its economic viability to synergize the production of biomethane and dimethyl ether from biogas. We conduct a profitability analysis based on the discounted cash flow method. The results revealed an unprofitable process with high cost/revenues ratios. Profitable scenarios would be reached by setting prohibitive DME prices (1983–5566 €/t) or very high feed-in tariffs subsidies (95.22 €/MWh in the best case scenario). From the cost reduction side, the analysis revealed the need of reducing investment costs. For this purpose, we propose a percentage of investment as incentive scheme. Although the size increase benefits cost/revenues ratio, only the 1000 m3/h biogas plant size will reach profitability if 90% of the investment is subsidized. A sensitivity analysis to check the influence of some important economical parameters is also included. Overall this study evidences the big challenge that our society faces in the way towards a circular economy. •Novel alternative for synergizing bio-methane and dimethyl ether production.•Profitability analysis for four different plant sizes.•The effect of dimethyl ether price and subsidies is studied.•The analysis revealed a technically viable but financially unprofitable process.•Evidence of the need of a strong green policy-making strategy.

Ziling Wang, Liang Huang, Tomas Ramirez Reina, Angelos M. Efstathiou, Qiang Wang (2020)Aqueous Miscible Organic LDH Derived Ni-Based Catalysts for Efficient CO2 Methanation, In: Catalysts101168 MDPI AG

Converting CO2 to methane via catalytic routes is an effective way to control the CO2 content released in the atmosphere while producing value-added fuels and chemicals. In this study, the CO2 methanation performance of highly dispersed Ni-based catalysts derived from aqueous miscible organic layered double hydroxides (AMO-LDHs) was investigated. The activity of the catalyst was found to be largely influenced by the chemical composition of Ni metal precursor and loading. A Ni-based catalyst derived from AMO-Ni3Al1-CO3 LDH exhibited a maximum CO2 conversion of 87.9% and 100% CH4 selectivity ascribed to both the lamellar catalyst structure and the high Ni metal dispersion achieved. Moreover, due to the strong Ni metal–support interactions and abundant oxygen vacancy concentration developed, this catalyst also showed excellent resistance to carbon deposition and metal sintering. In particular, high stability was observed after 19 h in CO2/H2 reaction at 360 °C.

Wei Jin, Laura Pastor-Pérez, Juan J Villora-Picó, M. Mercedes Pastor-Blas, José A Odriozola, Antonio Sepúlveda-Escribano, Tomás R Reina (2021)In-situ HDO of guaiacol over nitrogen-doped activated carbon supported nickel nanoparticles, In: Applied Catalysis. A, General118033 Elsevier B.V

In-situ hydrodeoxygenation of guaiacol over Ni-based nitrogen-doped activated carbon supported catalysts is presented in this paper as an economically viable route for bio-resources upgrading. The overriding concept of this paper is to use water as hydrogen donor for the HDO reaction, suppressing the input of external high-pressure hydrogen. The effect of nitrogen sources, including polypyrrole (PPy), polyaniline (PANI) and melamine (Mel) on the structural, electronic and ultimately of catalytic features of the designed materials have been addressed. Nitrogen-doped samples are more active than the undoped counterparts in the “H2-free” HDO process. For instance, the conversion of guaiacol increased by 8 % for Ni/PANI-AC compared to that of Ni/AC catalysts. The superior performance of Ni/NC can be attributed to the acid-base properties and modified electronic properties, which favours the C-O cleavage and water activation as well as enhances dispersion of Ni particles on the catalysts’ surface.

Francisco M Baena-Moreno, Estelle le Saché, Cameron Alexander Hurd Price, T.R Reina, Benito Navarrete (2021)From biogas upgrading to CO2 utilization and waste recycling: A novel circular economy approach, In: Journal of CO2 Utilization47101496 Elsevier Ltd

Herein a novel process to synergize biogas upgrading, CO2 utilization and waste recycling is proposed. Our study emerges as a promising strategy within the circular economy. In this work, the technical feasibility of Flue-Gas Desulfurization Gypsum as precipitant for definitely CO2 storage is studied. The precipitation stage is evaluated through two key factors: the quality of the carbonate product and the precipitation efficiency obtained. The physicochemical characterization of the solid carbonate product was analysed by means of Raman, X-Ray diffraction and scanning electron microscopy. The precipitation efficiency is evaluated through the variation of the main precipitation parameters (temperature, molar ratio and time). For this purpose, two groups of experiments were performed. The first group was aimed to model the precipitation system through experiments designed with DesignExpert vs.12 software. The second group of experiments allows to compare our results with pure species as precipitants, as well as to validate the model designed. The physicochemical characterization performed reveals high purity calcite as product. Encouraging precipitation efficiencies were obtained, ranging from 53.09–80.09% (66 % average). Furthermore, the model reveals a high influence of the molar ratio (3–5 times higher impact than other parameters) and low influence of temperature, which evidences the low energy consumption of the proposal. To optimize energy consumption, the model suggests 33 sets of parameters values. Examples of these values are 20 °C, 1.5 mol/mol, and 30 min, which allow to obtain a 72.57 % precipitation efficiency. Overall, this study confirms the technical feasibility of this circular economy approach.

Estelle le Saché, Panayiotis Tsaousis, Tomas Ramirez Reina, Enrique Ruiz-Trejo (2020)High Channel Density Ceramic Microchannel Reactor for Syngas Production, In: Energies (Basel)13(23) MDPI AG

Solid oxide fuel cells can operate with carbonaceous fuels, such as syngas, biogas, and methane, using either internal or external reforming, and they represent a more efficient alternative to internal combustion engines. In this work, we explore, for the first time, an alumina membrane containing straight, highly packed (461,289 cpsi), parallel channels of a few micrometers (21 mm) in diameter as a microreformer. As a model reaction to test the performance of this membrane, the dry reforming of methane was carried out using nickel metal and a composite nickel/ceria as catalysts. The samples with intact microchannels were more resistant to carbon deposition than those with a powdered sample, highlighting the deactivation mitigation effect of the microchannel structure. The coke content in the microchannel membrane was one order of magnitude lower than in the powder catalyst. Overall, this work is a proof of concept on the use of composite alumina membrane as microchannel reactors for high temperature reactions.

Francisco M. Baena-Moreno, Mónica Rodríguez-Galán, T. R. Reina, Zhien Zhang, Luis F. Vilches, Benito Navarrete (2019)Understanding the effect of Ca and Mg ions from wastes in the solvent regeneration stage of a biogas upgrading unit, In: Science of the Total Environment691pp. 93-100 Elsevier

This paper reveals the effect of calcium and magnesium ions in carbonation experiments carried out to regenerate sodium hydroxide from a biogas upgrading unit. This novel study arises as an alternative to standard physical process whose elevated energy consumption imposes economic restrictions. Previous works employed alkaline waste to turn them into value added product. Nevertheless, no attractive economical results were obtained due to the low regeneration efficiencies. Our hypothesis is that both calcium and magnesium waste composition percentages have an impact in the result, hence this work propose an isolated study aiming to determine the of each one in the global performance. To this end, the operational parameters (reaction time, reaction temperature and molar ratio) were tuned as well as physicochemical properties of the final solid samples were analysed by several techniques. The results indicate that calcium is much more prone than magnesium to reach high efficiencies in aqueous carbonation experiments. Additionally, higher quality products were achieved with calcium. The results of this study suppose an important step for understanding the aqueous carbonation through waste in the path to achieve a more sustainable city and society.

Run-Ping Ye, Lin Liao, Tomas Ramirez Reina, Jiaxu Liu, Durgaiah Chevella, Yonggang Jin, Maohong Fan, Jian Liu (2021)Engineering Ni/SiO₂ catalysts for enhanced CO₂ methanation, In: Fuel285119151 Elsevier

The CO₂ methanation is an important process in coal-to-gas, power-to-gas and CO₂ removal for spacecraft. Recently, metal-organic framework (MOF) derivatives have been demonstrated as high-performance catalysts for CO₂ upgrading processes. However, due to the high costs and low stability of MOF derivatives, it still remains challenge for the development of alternative synthesis methods avoiding MOF precursors. In this work, we present the sol-gel method for loading Ni-MOF to silica support in two-steps. Upon modifying the procedure, a more simplified one-step sol-gel method has been developed. Furthermore, the obtained Ni/SiO₂ catalyst still exhibits great catalytic performance with a CO₂ conversion of 77.2% and considerable CH4 selectivity of ~100% during a stability test for 52 h under a low temperature of 310 °C and high GHSV of 20,000 mL·g−1·h−1. Therefore, this work provides a ground-breaking direct strategy for loading MOF derived catalysts, and might shed a light on the preparation of highly dispersed Ni/SiO₂ catalyst.

Miriam González-Castaño, Estelle le Saché, Cameron Berry, Laura Pastor-Pérez, Harvey Arellano-García, Qiang Wang, Tomás R Reina (2021)Nickel Phosphide Catalysts as Efficient Systems for CO2 Upgrading via Dry Reforming of Methane, In: Catalysts11(4)446 MDPI

This work establishes the primordial role played by the support’s nature when aimed at the constitution of Ni2P active phases for supported catalysts. Thus, carbon dioxide reforming of methane was studied over three novel Ni2P catalysts supported on Al2O3, CeO2 and SiO2-Al2O3 oxides. The catalytic performance, shown by the catalysts’ series, decreased according to the sequence: Ni2P/Al2O3 > Ni2P/CeO2 > Ni2P/SiO2-Al2O3. The depleted CO2 conversion rates discerned for the Ni2P/SiO2-Al2O3 sample were associated to the high sintering rates, large amounts of coke deposits and lower fractions of Ni2P constituted in the catalyst surface. The strong deactivation issues found for the Ni2P/CeO2 catalyst, which also exhibited small amounts of Ni2P species, were majorly associated to Ni oxidation issues. Along with lower surface areas, oxidation reactions might also affect the catalytic behaviour exhibited by the Ni2P/CeO2 sample. With the highest conversion rate and optimal stabilities, the excellent performance depicted by the Ni2P/Al2O3 catalyst was mostly related to the noticeable larger fractions of Ni2P species established.

T Ramirez Reina, S Ivanova, V Idakiev, JJ Delgado, I Ivanov, T Tabakova, MA Centeno, JA Odriozola (2013)Impact of Ce-Fe synergism on the catalytic behaviour of Au/CeO2-FeOx/Al2O3 for pure H2 production, In: Catalysis Science and Technology3(3)pp. 779-787 The Royal Society of Chemistry

In this work the development of a series of gold catalysts, essentially based on γ-alumina promoted with a small superficial fraction of Ce–Fe mixed oxides, is reported. The catalytic behaviour is evaluated in the water gas shift reaction. The formation of a Ce–Fe solid solution is evidenced by XRD and related to the catalytic activity where the importance of the Ce–Fe interaction is demonstrated. The best catalyst reached CO conversions very close to the equilibrium limit. A long-term stability test is performed and the loss of activity is observed and attributed to reaction intermediates. Almost complete recovery of the initial conversion is achieved after oxidation treatment, suggesting that the problem of stability could be overcome by a suitable change in the reaction parameters thus leading to a highly efficient catalyst for future applications in H2 production and clean-up

T Ramirez Reina, E Papadopoulou, S Palma, S Ivanova, MA Centeno, T Ioannides, JA Odriozola (2014)Could an efficient WGS catalyst be useful in the CO-PrOx reaction?, In: Applied Catalysis B: Environmental150pp. 554-563

This work presents an evaluation of a high performance series of water gas shift (WGS) catalysts in the preferential CO oxidation reaction (PrOx) in order to examine the applicability of the same catalyst for both processes as a first step for coupling both reactions in a single process. Gold based catalysts are applied in an extensive study of the CO-PrOx reaction parameters, such as λ, WHSV, CO concentration and [H2O]/[CO2] ratio in order to obtain the best activity/selectivity balance. CO and H2 oxidation reactions were treated separately in order to establish the degree of CO/H2 oxidation competition. Additionally the catalysts behavior in the CO-PrOx parallel reactions such a WGS and RWGS have been also carried out to analyze their effect on product composition.

T Ramirez Reina, S Ivanova, MA Centeno, JA Odriozola (2013)Low Temperature CO oxidation on multicomponent gold based systems, In: Frontiers in Chemistry Frontiers Media

In this work the development of gold catalysts, essentially based on γ-alumina with small superficial fraction of Ce-Fe mixed oxides as support for the low temperature CO oxidation is proposed. Characterization results obtained by means of TEM, OSC, XPS, UV-Vis spectroscopy and H2-TPR are employed to correlate the activity data with the catalysts composition. The bare γ-alumina supported gold catalyst demonstrates the poorest activity within the series. The addition of CeO2 or FeOX improves the catalytic performance, especially observed for the CeO2-FeOx mixed oxide doped samples. This enhanced CO oxidation activity was related to the Ce-Fe interaction producing materials with promoted redox properties and therefore oxidation activity.

Francisco M. Baena-Moreno, Mónica Rodríguez-Galán, Fernando Vega, T.R. Reina, Luis F. Vilches, Benito Navarrete (2019)Synergizing carbon capture storage and utilization in a biogas upgrading lab-scale plant based on calcium chloride: Influence of precipitation parameters, In: Science of The Total Environment670pp. 59-66 Elsevier

Herein a strategy for biogas upgrading in a continuous flow absorption unit using CaCl2 as capturing agent is reported. This process is presented as an alternative to the standard physical regeneration processes to capture carbon dioxide (CO2) from biogas effluents with inherent high energy penalties. This work showcases a systematic study of the main parameters (reaction time, reaction temperature, and molar ratio reactant/precipitator) affecting calcium carbonate (CaCO3) precipitation efficiency in a reaction between sodium carbonate (Na2CO3) and CaCl2. In addition, the purity and main characteristics of the obtained product were carefully analysed via in a combined characterization study using Raman, XRD, and SEM. Our results indicate that acceptable precipitation efficiencies between 62 and 93% can be reached by fine tuning the studied parameters. The characterization techniques evidence pure CaCO3 in a calcite structure. These results confirmed the technical feasibility of this alternative biogas upgrading process through CaCO3 production.

Francisco M. Baena-Moreno, Mónica Rodríguez-Galán, Fernando Vega, T. R. Reina, Luis F. Vilches, Benito Navarrete (2019)Understanding the Influence of the Alkaline Cation K+ or Na+ in the Regeneration Efficiency of a Biogas Upgrading Unit, In: International Journal of Energy Research43(4)pp. 1578-1585 Wiley

This paper reveals a regeneration method for a carbonate compound after carbon dioxide (CO2) absorption in a biogas upgrading unit run with caustic mixtures, obtaining precipitated calcium carbonate (PCC) as valuable by-product. This process arises as an alternative to physical regeneration, which is highly energy intensive. This work provides novel insights on the regeneration efficiency of carbonates to hydroxides while also studying the influence of K+ or Na+ in the caustic CO2-trapping solution. The compared parameters were the reaction time, temperature and molar ratio. Moreover, psychochemical characterization of solids was obtained by means of Fourier-transform infrared spectroscopy (FTIR), Raman spectroscopy, X-ray powder diffraction (XRD) and Scanning Electron Microscopy (SEM) images. The results indicate that regeneration efficiencies are slightly lower when potassium is used instead of sodium, but quite acceptable for both of them. The chemical characterization experiments showed the predominance of calcium carbonate. Overall, the results obtained in this study proved that this process is feasible to upgrade biogas through PCC precipitation, which appears to be a promising economically viable process to synergise CCS and CCU.

Tomas Ramirez Reina, Laura Pastor Perez, V Patel, Estelle Le Saché (2019)CO2 methanation in the presence of methane: catalysts design and effect of methane concentration in the reaction mixture, In: Journal of the Energy Institute Elsevier

The work in this paper evidences the viability of producing synthetic natural gas (SNG) via the methanation reaction tackling two fundamental challenges on methanation catalysis (i) the development of advanced catalysts able to achieve high CO2 conversion and high methane yields and (ii) the unexplored effect of residual methane on the methanation stream. Both challenges have been successfully addressed using Ni/CeO2-ZrO2 catalysts promoted with Mn and Co. Mn does not seem to be a good promoter while Co prevents carbon deposition and secondary reactions. In fact, our Co-doped sample reached high levels of CO2 conversion and CH4 selectivity, especially at low reaction temperatures. In addition, this catalyst exhibits excellent catalytic behaviour when methane is introduced into the gas mixture, indicating its feasibility for further study to be conducted in realistic flue gases environments and methanation units with recycling loops. Furthermore, when methane is introduced in the reactant mixture, the Ni-Co/CeO2-ZrO2 sample is very stable maintaining high levels of conversion and selectivity. Overall our Co-doped catalyst can deliver high purity synthetic natural gas for long-term runs, promising results for gas-phase CO2 conversion units.

Vasileios Katranidis, Sai Gu, Tomas Ramirez Reina, Esat Alpay, B Allcock, S Kamnis (2017)Experimental study of high velocity oxy-fuel sprayed WC-17Co coatings applied on complex geometries. Part B: Influence of kinematic spray parameters on microstructure, phase composition and decarburization of the coatings, In: Surface and Coatings Technology328pp. 499-512 Elsevier

The aim of this study is to evaluate comprehensively the effect of spray angle, spray distance and gun traverse speed on the microstructure and phase composition of HVOF sprayed WC-17 coatings. An experimental setup that enables the isolation of each one of the kinematic parameters and the systemic study of their interplay is employed. A mechanism of particle partition and WC-cluster rebounding at short distances and oblique spray angles is proposed. It is revealed that small angle inclinations benefit notably the WC distribution in the coatings sprayed at long stand-off distances. Gun traverse speed, affects the oxygen content in the coating via cumulative superficial oxide scales formed on the as-sprayed coating surface during deposition. Metallic W continuous rims are seen to engulf small splats, suggesting crystallization that occurred in-flight.

T Ramirez Reina, P Yeletski, JM Bermudez, P Arcelus-Arrillaga, VA Yakovlev, M Millan (2015)Anthracene Aquacracking Using NiMo/SiO2 Catalysts in Supercritical Water Conditions, In: Proceddings of 2015 AIChE Annual Meeting

The current status of world oil reserves is a contentious matter, but it is widely accepted that conventional resources are dwindling and their reserves are less easily accessible [1]. Therefore, the production of heavy crude oil (HCO), which is the remnant of conventional oil has become more relevant and will remain so in the foreseeable future [2]. In this sense, there is a need for more efficient refining processes to transform HCO into lighter fuels. Conventional processes for increasing the value of heavy oil fractions aim to increase the H/C ratio of fuel, generating lighter fractions. However, this implies either rejecting a large amount of the carbon in the feed as in thermal and catalytic cracking processes, or using high pressure hydrogen, an expensive gas, in hydrocracking processes [3].

Estelle Le Saché, Sarah Johnson, Laura Pastor-Pérez, Bahman Amini Horri, Tomas Reina (2019)Biogas Upgrading Via Dry Reforming Over a Ni-Sn/CeO2-Al2O3 Catalyst: Influence of the Biogas Source, In: Energies12(6) MDPI

Biogas is a renewable, as well as abundant, fuel source which can be utilised in the production of heat and electricity as an alternative to fossil fuels. Biogas can additionally be upgraded via the dry reforming reactions into high value syngas. Nickel-based catalysts are well studied for this purpose but have shown little resilience to deactivation caused by carbon deposition. The use of bi-metallic formulations, as well as the introduction of promoters, are hence required to improve catalytic performance. In this study, the effect of varying compositions of model biogas (CH4/CO2 mixtures) on a promising multicomponent Ni-Sn/CeO2-Al2O3 catalyst was investigated. For intermediate temperatures (650 °C), the catalyst displayed good levels of conversions in a surrogate sewage biogas (CH4/CO2 molar ratio of 1.5). Little deactivation was observed over a 20 h stability run, and greater coke resistance was achieved, related to a reference catalyst. Hence, this research confirms that biogas can suitably be used to generate H2-rich syngas at intermediate temperatures provided a suitable catalyst is employed in the reaction.

J Santos, Tomas Ramirez Reina, I Ivanov, A Penkova, S Ivanova, T Tabakova, M Centeno, V Idakiev, J Odriozola (2018)Multicomponent Au/Cu-ZnO-Al2O3 catalysts: Robust materials for clean hydrogen production, In: Applied Catalysis A: General558pp. 91-98 Elsevier

Clean hydrogen production via WGS is a key step in the development of hydrogen fuel processors. Herein, we have designed a new family of highly effective catalysts for low-temperature WGS reaction based on gold modified copper-zinc mixed oxides. Their performance was controlled by catalysts’ composition and the Au-Cu synergy. The utilization of hydrotalcite precursors leads to an optimal microstructure that ensures excellent Au and Cu dispersion and favors their strong interaction. From the application perspective these materials succeed to overcome the major drawback of the commercial WGS catalysts: resistance towards start/stop operations, a mandatory requisite for H2-powered mobile devices.

L. Pastor-Pérez, F. Baibars, E. Le Sache, Harvey Arellano-Garcia, Sai Gu, Tomas Ramirez Reina (2017)CO2 valorisation via Reverse Water-Gas Shift reaction using advanced Cs doped Fe-Cu/Al2O3 catalysts, In: Journal of CO2 Utilization21pp. 423-428 Elsevier

This paper evidences the viability of chemical recycling of CO2 via reverse water-gas shift reaction using advanced heterogeneous catalysts. In particular, we have developed a multicomponent Fe-Cu-Cs/Al2O3 catalyst able to reach high levels of CO2 conversions and complete selectivity to CO at various reaction conditions (temperature and space velocities). In addition, to the excellent activity, the novel-Cs doped catalyst is fairly stable for continuous operation which suggests its viability for deeper studies in the reverse water-gas shift reaction. The catalytic activity and selectivity of this new material have been carefully compared to that of Fe/Al2O3, Fe-Cu/Al2O3 and Fe-Cs/Al2O3 in order to understand each active component’s contribution to the catalyst’s performance. This comparison provides some clues to explain the superiority of the multicomponent Fe-Cu-Cs/Al2O3 catalyst

E. Le Saché, L. Pastor-Perez, D. Watson, A. Sepúlveda-Escribano, T. R. Reina (2018)Ni stabilised on inorganic complex structures: superior catalysts for chemical CO2 recycling via dry reforming of methane, In: Applied Catalysis B: Environmental236pp. 458-465 Elsevier

CO2 utilisation is becoming an appealing topic in catalysis science due to the urgent need to deal with greenhouse gases (GHG) emissions. Herein, the dry reforming of methane (DRM) represents a viable route to convert CO2 and CH4 (two of the major GHG) into syngas, a highly valuable intermediate in chemical synthesis. Nickel-based catalysts are economically viable materials for this reaction, however they show inevitable signs of deactivation. In this work stabilisation of Ni in a pyrochlore-perovskite structure is reported as a viable method to prevent fast deactivation. Substitution of Zirconium by Ni at various loadings in the lanthanum zirconate pyrochlore La2Zr2O7 is investigated in terms of reactant conversions under various reaction conditions (temperature and space velocity). XRD analysis of the calcined and reduced catalysts showed the formation of crystalline phases corresponding to the pyrochlore structure La2Zr2-xNixO7-δ and an additional La2NiZrO6 perovskite phase at high Ni loadings. Carbon formation is limited using this formulation strategy and, as a consequence, our best catalyst shows excellent activity for DRM at temperatures as low as 600 °C and displays great stability over 350 hours of continuous operation. Exsolution of Ni from the oxide structure, leading to small and well dispersed Ni clusters, could explain the enhanced performance.

Qi Zhang, Laura Pastor Perez, Wei Jin, Sai Gu, Tomas Ramirez Reina (2019)Understanding the promoter effect of Cu and Cs over highly effective -Mo2C catalysts for the reverse water-gas shift reaction, In: Applied Catalysis B: Environmental244pp. 889-898 Elsevier

Mo2C is an effective catalyst for chemical CO2 upgrading via reverse water-gas shift (RWGS). In this work, we demonstrate that the activity and selectivity of this system can be boosted by the addition of promoters such as Cu and Cs. The addition of Cu incorporates extra active sites such as Cu+ and Cu0 which are essential for the reaction. Cs is an underexplored dopant whose marked electropositive character generates electronic perturbations on the catalyst’s surface leading to enhanced catalytic performance. Also, the Cs-doped catalyst seems to be in-situ activated due to a re-carburization phenomenon which results in fairly stable catalysts for continuous operations. Overall, this work showcases a strategy to design highly efficient catalysts based on promoted β-Mo2C for CO2 recycling via RWGS.

Elham Ketabchi, Laura Pastor Perez, Tomas Ramirez Reina, Harvey Arellano-Garcia (2019)Catalytic upgrading of acetone, butanol and Ethanol (ABE): A step ahead for the production of added value chemicals in bio-refineries, In: ACS Sustainable Chemistry and Engineering American Chemical Society
E. Le Saché, L. Pastor-Pérez, V. Garcilaso, D.J. Watson, M.A. Centeno, J.A. Odriozola, T.R. Reina (2019)Flexible syngas production using a La2Zr2O7-δ pyrochlore-double perovskite catalyst: Towards a direct route for gas phase CO2 recycling, In: Catalysis Today Elsevier

The bi-reforming of methane (BRM) has the advantage of utilising greenhouse gases and producing H2 rich syngas. In this work Ni stabilised in a pyrochlore-double perovskite structure is reported as a viable catalyst for both Dry Reforming of Methane (DRM) and BRM. A 10 wt.% Ni-doped La2Zr2O7 pyrochlore catalyst was synthesised, characterised and tested under both reaction conditions and its performance was compared to a supported Ni/La2Zr2O7. In particular the effect of steam addition is investigated revealing that steam increases the H2 content in the syngas but limits reactants conversions. The effect of temperature, space velocity and time on stream was studied under BRM conditions and brought out the performance of the material in terms of activity and stability. No deactivation was observed, in fact the addition of steam helped to mitigate carbon deposition. Small and well dispersed Ni clusters, possibly resulting from the progressive exsolution of Ni from the mixed oxide structure could explain the enhanced performance of the catalyst.

JA Odriozola, T Ramirez Reina, MA Centeno, A Ivanova, V Idakiev, T Tabakova (2013)Gold catalysts and the use thereof in the water-gas shift reaction

The present invention relates to a substrate for a gold catalyst, of formula CeO2 - ΜΟχ/ΑΙ2O3, wherein the substrate comprises between 60 and 90% w/w of Al2O3 and a percentage of CeO2 between 10 and 40% w/w, optionally doped with MOx oxide, with M selected from Fe, Zn, Co and Ni, Zr or mixtures thereof. The present invention relates to the use of the catalyst for the water-gas shift reaction and, more particularly, the use thereof in fuel cells.

E. le Saché, J.L. Santos, T.J. Smith, Harvey Arellano-Garcia, J.A. Odriozola, Tomas Ramirez Reina (2018)Multicomponent Ni-CeO2 Nanocatalysts for Syngas production from CO2/CH4 mixtures, In: Journal of CO2 Utilization25pp. 68-78 Elsevier

The dry reforming of methane with CO2 is a common route to transform CO2/CH4 mixtures into added value syngas. Ni based catalysts are highly active for this goal but suffer from deactivation, as such promoters need to be introduced to counteract this, and improve performance. In this study, mono- and bi-metallic formulations based on 10 wt.% Ni/CeO2-Al2O3 are explored and compared to a reference 10 wt.% Ni/γ-Al2O3. The effect of Sn and Pt as promoters of Ni/CeO2-Al2O3 was also investigated. The formulation promoted with Sn looked especially promising, showing CO2 conversions stabilising at 65% after highs of 95%. Its increased performance is attributed to the additional dispersion Sn promotion causes. Changes in the reaction conditions (space velocity and temperature) cement this idea, with the Ni-Sn/CeAl material performing superiorly to the mono-metallic material, showing less deactivation. However, in the long run it is noted that the mono-metallic Ni/CeAl performs better. As such the application is key when deciding which catalyst to employ in the dry reforming process.

Tomas Ramirez Reina, Utsab Guharoy, Emilia Olsson, Sai Gu, Qiong Cai (2019)Theoretical insights of Ni2P (0001) surface towards its potential applicability in CO2 conversion via dry reforming of methane, In: ACS Catalysis9(4)pp. 3487-3497 American Chemical Society

This study reports the potential application of Ni2P as highly effective catalyst for chemical CO2 recycling via dry reforming of methane (DRM). Our DFT calculations reveal that the Ni2P (0001) surface is active towards adsorption of the DRM species, with the Ni hollow site being the most energetically stable site and Ni-P and P contributes as co-adsorption sites in DRM reaction steps. Free energy analysis at 1000 K found CH-O to be the main pathway for CO formation. The competition of DRM and reverse water gas shift (RWGS) is also evidenced with the latter becoming important at relatively low reforming temperatures. Very interestingly oxygen seems to play a key role in making this surface resistant towards coking. From microkinetic analysis we have found greater oxygen surface coverage than that of carbon at high temperatures which may help to oxidize carbon deposits in continuous runs. The tolerance of Ni2P towards carbon deposition was further corroborated by DFT and micro kinetic analysis. Along with the higher probability of C oxidation we identify poor capacity of carbon diffusion on the Ni2P (0001) surface with very limited availability of C nucleation sites. Overall, this study opens new avenues for research in metal-phosphide catalysis and expands the application of these materials to CO2 conversion reactions.

Vasileios Katranidis, Sai Gu, Tomas Ramirez Reina, Esat Alpay, Bryan Allcock, Spyros Kamnis (2017)Experimental study of high velocity oxy-fuel sprayed WC-17Co coatings applied on complex geometries. Part B: Influence of kinematic spray parameters on microstructure, phase composition and decarburization of the coatings, In: Surface & Coatings Technology328pp. 499-512 Elsevier

The aim of this study is to evaluate comprehensively the effect of spray angle, spray distance and gun traverse speed on the microstructure and phase composition of HVOF sprayed WC-17 coatings. An experimental setup that enables the isolation of each one of the kinematic parameters and the systemic study of their interplay is employed. A mechanism of particle partition and WC-cluster rebounding at short distances and oblique spray angles is proposed. It is revealed that small angle inclinations benefit notably the WC distribution in the coatings sprayed at long stand-off distances. Gun traverse speed, affects the oxygen content in the coating via cumulative superficial oxide scales formed on the as-sprayed coating surface during deposition. Metallic W continuous rims are seen to engulf small splats, suggesting crystallization that occurred in-flight.

M Millan, T Ramirez Reina, JM Bermudez, H Puron, JL Pinilla (2016)CATALYST FOR PROCESSING HEAVY OILS AND ITS PREPARATION METHOD
Shawn C. Rood, Huseyin B. Ahmet, Anais Gomez-Ramon, Laura Torrente-Murciano, Tomas R. Reina, Salvador Eslava (2018)Enhanced Ceria Nanoflakes using Graphene Oxide as a Sacrificial Template for CO Oxidation and Dry Reforming of Methane, In: Applied Catalysis B: Environmental242pp. 358-368 Elsevier

The development of novel fabrication methods to produce ceria catalysts with good high-temperature stability is critical for their implementation across a range of different applications. Herein, graphene oxide flakes are used as a sacrificial template in the synthesis of ceria particles to replicate the graphene oxide’s two-dimensionality. While performing the synthesis without graphene oxide results in large agglomerations of ceria crystallites, the addition of graphene oxide during the synthesis results in ceria nanoflakes (< 10 nm) replicating the graphene oxide morphology. This novel shape limits the diffusion of atoms at high temperature to a two-dimensional plane which is translated into a low sintering degree and consequently, an enhanced thermal stability. In this way, the ceria flakes are capable of maintaining high surface areas after calcination at high temperatures (> 400 °C) which results in improved catalytic performance for the oxidation of carbon monoxide. This resistance versus sintering has also a beneficial effect when ceria flakes are used as catalytic support of nickel particles. Improved metal dispersion and high metal-support interaction leads to lower sintering during the dry reforming of methane than similarly prepared un-templated ceria nickel catalysts. These results demonstrate the advantage of using graphene oxide as a sacrificial template for the production of sintering-resistant catalysts with good catalytic performance at high temperatures.

T Ramirez Reina, W Xu, S Ivanova, MA Centeno, J Hanson, JA Rodriguez, JA Odriozola (2012)Operando characterization of iron-promoted ceria-alumina gold catalysts during the water-gas shift reaction
Francisco Baena, Juan Daniel Sebastia Saez, Qiang Wang, Tomas Ramirez Reina (2020)Is the production of biofuels and bio-chemicals always profitable? Co-production of biomethane and urea from biogas as case study., In: Energy Conversion and Management Elsevier

In this paper we present a techno-economic analysis of a novel route for biomethane – urea co-production from biogas. The idea emerges as an alternative path for improving the profitability of biogas upgrading plants. The profitability of four different biogas plant sizes (100, 250, 500, and 1000 m3/h) in four European countries (Spain, Italy, United Kingdom and Germany) is studied under the current policy schemes for biomethane production of each country. Our study evidences that with the present policy schemes for biomethane production, only medium and large scale plants (500 and 1000 m3/h) in Italy would be profitable. The reason is the current strong support for biomethane production in Italy through feed-in tariffs subsidies. In this sense, we analysed the potential benefits of governmental incentives through bio-methane subsidies (feed-in tariffs and investment percentage). Feed-in tariffs proved to be a worthwhile solution for large plants. Indeed, profitability is reached under subsidies of 30-48 €/MWh. Overall, plants located in southern EU countries are more likely to reach profitability with lower subsidies. The potential of costs reduction (i.e. ammonia price) was also analysed, showing that cutting-down production costs is essential to reduce the amount of subsidies received. In summary, our study shows the challenge that European policies face in the path towards a bio-based economy using biogas upgrading as reference case.

Francisco Baena-Moreno, Mónica Rodríguez-Galán, Fernando Vega, T. Reina, Luis Vilches, Benito Navarrete (2018)Regeneration of Sodium Hydroxide from a Biogas Upgrading Unit through the Synthesis of Precipitated Calcium Carbonate: An Experimental Influence Study of Reaction Parameters, In: Processes6(11) MDPI

This article presents a regeneration method of a sodium hydroxide (NaOH) solution from a biogas upgrading unit through calcium carbonate (CaCO3) precipitation as a valuable by-product, as an alternative to the elevated energy consumption employed via the physical regeneration process. The purpose of this work was to study the main parameters that may affect NaOH regeneration using an aqueous sodium carbonate (Na2CO3) solution and calcium hydroxide (Ca(OH)2) as reactive agent for regeneration and carbonate slurry production, in order to outperform the regeneration efficiencies reported in earlier works. Moreover, Raman spectroscopy and Scanning Electron Microscopy (SEM) were employed to characterize the solid obtained. The studied parameters were reaction time, reaction temperature, and molar ratio between Ca(OH)2 and Na2CO3. In addition, the influence of small quantities of NaOH at the beginning of the precipitation process was studied. The results indicate that regeneration efficiencies between 53%–97% can be obtained varying the main parameters mentioned above, and also both Raman spectroscopy and SEM images reveal the formation of a carbonate phase in the obtained solid. These results confirmed the technical feasibility of this biogas upgrading process through CaCO3 production.

Francisco M. Baena-Moreno, Laura Pastor-Pérez, Zhien Zhang, T.R. Reina (2020)Stepping towards a low-carbon economy. Formic acid from biogas as case of study, In: Applied Energy268115033 Elsevier

The European Union has set an ambitious plan for addressing the Global Challanges in the coming years. One of these challenges is the use of biomass and the production of biomass-derived products following the spirit of a circular economy. Biogas obtained from biomass anaerobic digestion could play a pivotal role in this strategy. Herein an innovative strategy for synergizing biogas upgrading to biomethane and formic acid production from CO2 is presented. A profitability analysis of the combined biogas upgrading – CO2 utilization process was conducted to assess the economic viability of this novel approach. The profitability study focuses mainly on net present value and profitability index. Even though the process is environmentally favourable, negative profitability results are obtained. To revert the negative outputs, out of the market formic acid prices (1767–3135 €/t) would be needed to achieve a net present value equal to zero. The alternative of feed-in tariffs biomethane subsidies needs high values (121.1–269.4 €/MW) to reach profitable scenarios. These unsuccessful profitability results are ascribed to high consumables costs, mainly associated with the catalytic conversion of a CO2-rich feedstock. A 80% reduction of catalysts costs can considerably improve net present value up to 50%. This result indicates that further research is needed to find econimocally appealing catalysts to perform this process. The effect of biomethane subsidies as percentage of investment was also considered, evidencing encouraging results for small scale plants.

T Ramirez Reina, A Álvarez, S del Valle, S Ivanova, F Romero-Sarria, MA Centeno, JA Odriozola (2013)Influence of the Lanthanide Oxides on the Catalytic Behavior of Au/Al2O3 Catalysts for Total and Preferential CO Oxidation, In: Advanced Chemistry Letters1(3)pp. 237-246

In this work the influence of the lanthanide series oxide addition to gold supported alumina catalyst is discussed. A clear promoting effect was observed no matter the employed reaction. Nevertheless, the presence of hydrogen in the oxidation mixture reveals interesting dissimilarities within the series of studied oxides. The differences in the catalytic behaviour of the samples are correlated to the crystal structure variations, oxygen sub-lattice disorder, gold presence and oxide's ability to undergo hydration/dehydration reactions.

Cameron Price, Emily Earles, Laura Pastor-Perez, Jian Liu, Tomas Ramirez Reina (2018)Advantages of Yolk Shell Catalysts for the DRM: A Comparison of Ni/ZnO@SiO2 vs. Ni/CeO2 and Ni/Al2O3., In: Chemistry1(1)pp. 3-16 MDPI

Encapsulation of metal nanoparticles is a leading technique used to inhibit the main deactivation mechanisms in dry reforming of methane reaction (DRM): Carbon formation and Sintering. Ni catalysts (15%) supported on alumina (Al2O3) and ceria (CeO2) have shown they are no exception to this analysis. The alumina supported catalysts experienced graphitic carbonaceous deposits, whilst the ceria showed considerable sintering over 15 h of DRM reaction. The effect of encapsulation compared to that of the performance of uncoated catalysts for DRM reaction has been examined at different temperatures, before conducting longer stability tests. The encapsulation of Ni/ZnO cores in silica (SiO2) leads to advantageous conversion of both CO2 and CH4 at high temperatures compared to its uncoated alternatives. This work showcases the significance of the encapsulation process and its overall effects on the catalytic performance in chemical CO2 recycling via DRM.

T Ramirez Reina, AA Moreno, S Ivanova, JA Ordriozola, MA Centeno (2012)Influence of Vanadium or Cobalt Oxides on the CO Oxidation Behavior of Au/MOx/CeO2–Al2O3 Systems, In: ChemCatChem4(4)pp. 512-520

A series of V2O5- and Co3O4-modified ceria/alumina supports and their corresponding gold catalysts were synthesized and their catalytic activities evaluated in the CO oxidation reaction. V2O5-doped solids demonstrated a poor capacity to abate CO, even lower than that of the original ceria/alumina support, owing to the formation of CeVO4. XRD, Raman spectroscopy, and H2-temperature programmed reduction studies confirmed the presence of this stoichiometric compound, in which cerium was present as Ce3+ and its redox properties were avoided. Co3O4-doped supports showed a high activity in CO oxidation at subambient temperatures. The vanadium oxide-doped gold catalysts were not efficient because of gold particle agglomeration and CeVO4 formation. However, the gold–cobalt oxide–ceria/alumina catalysts demonstrated a high capacity to abate CO at and below room temperature. Total conversion was achieved at −70 °C. The calculated apparent activation energy values revealed a theoretical optimum loading of a half-monolayer.

Daniel Sebastia-Saez, Tomas Ramirez Reina, Ravi Silva, Harvey Arellano-Garcia (2019)Synthesis and characterisation of n-octacosane@silica nano-capsules for thermal storage applications, In: International Journal of Energy Research Wiley

This work reports the synthesis and characterisation of a core-shell n-octacosane@silica nano-encapsulated phase-change material obtained via interfacial hydrolysis and poly-condensation of tetraethyl orthosilicate in mini-emulsion. Silica has been used as the encapsulating material because of its thermal advantages relative to synthesised polymers. The material presents excellent heat storage potential, with a measured latent heat varying between 57.1 and 89 kJ∙kg-1 (melting point between 58 and 64°C) and a small particle size (between ~565 and ~227 nm). Degradation of the n-octacosane core starts between 150 and 180°C. Also, the use of silica as shell material gives way to a heat conductivity of 0.796 W∙m-1∙K-1 (greater than that of nano-encapsulated materials with polymeric shell). Charge/discharge cycles have been successfully simulated at low pressure to prove the suitability of the nano-powder as phase-change material. Further investigations will be carried out in the future regarding the use of the synthesised material in thermal applications involving nanofluids.

L. Yang, L. Pastor-Pérez, S. Gu, A. Sepúlveda-Escribano, T. R. Reina (2018)Highly efficient Ni/CeO2-Al2O3 catalysts for CO2 upgrading via Reverse Water-Gas Shift: Effect of selected transition metal promoters, In: Applied Catalysis B: Environmental232pp. 464-471 Elsevier

In the context of Carbon Capture and Utilisation (CCU), the catalytic reduction of CO2 to CO via reverse water-gas shift (RWGS) reaction is a desirable route for CO2 valorisation. Herein, we have developed highly effective Ni-based catalysts for this reaction. Our study reveals that CeO2-Al2O3 is an excellent support for this process helping to achieve high degrees of CO2 conversions. Interestingly, FeOx and CrOx, which are well-known active components for the forward shift reaction, have opposite effects when used as promoters in the RWGS reaction. The use of iron remarkably boosts the activity, selectivity and stability of the Ni-based catalysts, while adding chromium results detrimental to the overall catalytic performance. In fact, the iron-doped material was tested under extreme conditions (in terms of space velocity) displaying fairly good activity/stability results. This indicates that this sort of catalysts could be potentially used to design compact RWGS reactors for flexible CO2 utilisation units.

Tomas Ramirez Reina, J. Liu, S. Ivanova (2020)Editorial: Catalysis by Gold for Gas & Liquid Phase Reactions: A Golden Future for Environmental Catalysis., In: Frontiers in Chemistry Frontiers In
Cameron Price, William Arnold, Laura Pastor-Perez, Bahman Amini-Horri, Thomas R. Reina (2020)Catalytic upgrading of a biogas model mixture via low temperature DRM using multicomponent catalysts., In: Topics in Catalysis Springer Verlag

The catalytic performance of a series of bimetallic Ni-Co/CeO2-Al2O3 catalysts were evaluated within the dry reforming of methane (DRM) reaction, commonly used for upgrading biogas. The study focused on the variation of CeO2 weight loadings between 0, 10, 20 and 30%. It was found that the addition of CeO2 promoted CH4 and CO2 conversion across the temperature range and increased H2/CO ratio for the “low temperature” DRM. X-Ray Diffraction (XRD), H2-Temperature Programmed Reduction (H2-TPR) and X-Ray Photoelectron Spectroscopy (XPS) analysis revealed the formation of Ce4+ during activation of the 30% sample, resulted in excessive carbon deposition during reaction. The lowest CeO2 weight loadings exhibited softer carbon formation and limited increased chemical stability during reaction at the expense of activity. Of the tested weight loadings, 20 wt% CeO2 exhibited the best balance of catalytic activity, chemical stability and deactivation resistance in the DRM reaction. Hence this catalyst can be considered a promising system for syngas production from biogas at relatively low temperatures evidencing the pivotal role of catalysts design to develop economically viable processes for bioresources valorisation.

Elham Ketabchi, Laura Pastor-Perez, Harvey Arellano-Garcia, Tomas Romarez Reina (2020)Influence of Reaction Parameters on the Catalytic Upgrading of an Acetone, Butanol and Ethanol (ABE) Mixture: Exploring New Routes for Modern Biorefineries., In: Frontiers in Chemistry Frontiers In

Here we present a comprehensive study on the effect of reaction parameters on the upgrade of an acetone, butanol and ethanol mixture – key molecules and platform products of great interest within the chemical sector. Using a selected high performing catalyst, Fe/MgO-Al2O3, the variation of temperature, reaction time, catalytic loading and reactant molar ratio have been examined in this reaction. This work is aiming to not only optimise the reaction conditions previously used, but to step towards using less energy, time and material by testing those conditions and analysing the sufficiency of the results. Herein we demonstrate that this reaction is favored at higher temperatures and longer reaction time. Also, we observe that increasing the catalyst loading had a positive effect on the product yields, while reactant ratios have shown to produce varied results due to the role of each reactant in the complex reaction network. In line with the aim of reducing energy and costs, this work showcases that the products from the upgrading route have significantly higher market value than the reactants, highlighting this process represents an appealing route to be implemented in modern biorefineries.

T Ramirez Reina, C Megias-Sayago, A Perez, S Ivanova, MA Centeno, JA Odriozola (2015)H2 oxidation as criterion for PrOx catalyst selection: examples based on Au-CoOx supported systems, In: Journal of Catalysispp. 161-171

A new approach for understanding PrOx reaction over gold catalysts is proposed in this work. The competition between H2 and CO oxidation has been studied over a series of Au/MOx/Al2O3 (M = Ce and Co) catalysts in simulated post-reforming gas stream, containing H2O and CO2 for H2 cleanup goals. The catalysts' behavior is correlated to their oxygen storage capacity, redox behavior, and oxidation ability. The estimation of the reaction rates reveals that in these solids the H2 combustion, the selectivity limiting factor in the PrOx process, is mainly controlled by the support and not by the gold presence. The possible use of the hydrogen oxidation reaction as a catalyst selection criterion is discussed

T Ramirez Reina, S Ivanova, MI Domínguez, MA Centeno, JA Odriozola (2012)Sub-ambient CO oxidation over Au/MOx/CeO2-Al2O3 (M=Zn or Fe), In: Applied Catalysis A: General419pp. 58-66

A series of ZnO and Fe2O3 modified ceria/alumina supports and their corresponding gold catalyst were prepared and studied in the CO oxidation reaction. ZnO-doped solids show a superior catalytic activity compared to the bare CeO2-Al2O3, which is attributed to the intimate contact of the ZnO and CeO2 phases, since an exchange of the lattice oxygen occurs at the interface. In a similar way, Fe2O3-modified supports increase the ability of the CeO2-Al2O3 solids to eliminate CO caused by both the existence of Ce–Fe contact surface and the Fe2O3 intrinsic activity. All of the gold catalysts were very efficient in oxidising CO irrespective of the doping metal oxide or loading, with the ZnO containing systems better than the others. The majority of the systems reached total CO conversion below room temperature with the ZnO and Fe2O3 monolayer loaded systems the most efficient within the series.

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 (2019)Phenanthrene catalytic cracking in Supercritical Water: effect of the reaction medium on NiMo/SiO2 catalysts, In: Catalysis Today329pp. 197-205 Elsevier

A series of NiMo/SiO2 catalysts was synthesized by sol-gel method for heavy oil upgrading in supercritical water (SCW). Phenanthrene was used as substrate as it represents polyaromatic structures present in asphaltenes. No phenanthrene conversion was observed in a blank (non-catalytic) experiment. However, phenanthrene conversions up to 24 % after 1 h of reaction in SCW at 425 °C and 230 bar were observed in the presence of NiMo/SiO2, underlining the role of the catalysts in the process. Conversion was found to be dependent mainly on Ni content and the Ni/Mo ratio in the catalysts. The liquid products obtained are thought to be the result of both oxidation and hydrogenation processes. Characterization of the fresh and spent catalysts using X-ray diffraction (XRD), transmission electron microscopy (TEM) and X-ray photoelectron spectroscopy (XPS) was performed. It was revealed that catalysts are not completely stable in SCW, showing that NiMo intermetallic compounds formed the initial catalysts were decomposed, Mo0 and Ni0 were oxidised and the latter formed Ni2SiO4. In addition, MoO2 phase domain size in the catalysts increased and the surface of the spent catalysts appeared to be enriched with Ni and depleted with Mo.

J. Yu, J.A. Odriozola, T. R. Reina (2019)Dry Reforming of Ethanol and Glycerol: Mini-Review., In: Catalysts9(12)1015 MDPI AG

Dry reforming of ethanol and glycerol using CO2 are promising technologies for H2 production while mitigating CO2 emission. Current studies mainly focused on steam reforming technology, while dry reforming has been typically less studied. Nevertheless, the urgent problem of CO2 emissions directly linked to global warming has sparked a renewed interest on the catalysis community to pursue dry reforming routes. Indeed, dry reforming represents a straightforward route to utilize CO2 while producing added value products such as syngas or hydrogen. In the absence of catalysts, the direct decomposition for H2 production is less efficient. In this mini-review, ethanol and glycerol dry reforming processes have been discussed including their mechanistic aspects and strategies for catalysts successful design. The effect of support and promoters is addressed for better elucidating the catalytic mechanism of dry reforming of ethanol and glycerol. Activity and stability of state-of-the-art catalysts are comprehensively discussed in this review along with challenges and future opportunities to further develop the dry reforming routes as viable CO2 utilization alternatives.

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