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Frontiers in Catalysis for CO2 Methanation
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Frontiers in Catalysis for CO2 Methanation

A special issue of Catalysts (ISSN 2073-4344). This special issue belongs to the section "Environmental Catalysis".

Deadline for manuscript submissions: closed (31 January 2023) | Viewed by 19729

Special Issue Editor

Prof. Dr. Wojciech Gac

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Guest Editor
Department of Chemical Technology, Faculty of Chemistry, Maria Curie-Skłodowska University, 20-031 Lublin, Poland
Interests: catalysts CO2 methanation; hydrogen; methanol, ethanol; oxidation; methane; spectroscopy
Special Issues, Collections and Topics in MDPI journals

Special Issue Information

Dear Colleagues, 

Methanation of CO2 is perceived today as the response to the urgent challenges of the modern economy, which include more effective and sustainable utilisation of fossil fuels, production of energy and chemical products by the application of renewable resources and captured waste CO2, reducing the rate of global warming.

Although the catalytic conversion of CO2 to methane, known as the Sabatier process, was developed at the beginning of the 20th century, fundamental and applied research studies on complex surface phenomena, such as activation of CO2 and H2 molecules, their transformation into surface species, new catalysts formulas, deactivation of catalysts by sintering, carbon deposition and poisoning using new computational and advanced experimental methods are still required. CO2 methanation is a highly exothermic reaction, the composition of the feed stream may vary over time or can be contaminated with various compounds, hence the presentation of new theoretical and experimental results concerning the course of the methanataion reaction, demonstration of innovative synthesis methods, catalysts with a new chemical composition or microstructure, allowing to improve the activity and selectivity at low temperatures, and on the other hand, durability at high temperatures,  resistance to sintering or poisoning, as well as the discussion on the development of new types of reactors with improved heat and mas transfer, integrated with associated processes, including co-electrolysis or biogas valorization, may be essential for further progress. Such goals can be achieved, e.g. by the application of supports with specific structural, acid-base or redox properties, stabilisation of noble or non-noble small metal nanoparticles within porous oxide materials, introducing of promoters and modifiers, formation of alloys, synthesis of catalysts based on organometallic systems, as well as development of new catalysts designed for microstructured, membrane or photocatalytic reactors. 

The main objective of the Special Issue entitled “Frontiers in Catalysis for CO2 Methanation” is to present a wide spectrum of the latest achievements in the field of catalytic conversion of carbon dioxide to methane. I hope that the presented series of articles will become a platform for further discussion and development.

Prof. Wojciech Gac
Guest Editor

Manuscript Submission Information

Manuscripts should be submitted online at www.mdpi.com by registering and logging in to this website. Once you are registered, click here to go to the submission form. Manuscripts can be submitted until the deadline. All submissions that pass pre-check are peer-reviewed. Accepted papers will be published continuously in the journal (as soon as accepted) and will be listed together on the special issue website. Research articles, review articles as well as short communications are invited. For planned papers, a title and short abstract (about 100 words) can be sent to the Editorial Office for announcement on this website.

Submitted manuscripts should not have been published previously, nor be under consideration for publication elsewhere (except conference proceedings papers). All manuscripts are thoroughly refereed through a single-blind peer-review process. A guide for authors and other relevant information for submission of manuscripts is available on the Instructions for Authors page. Catalysts is an international peer-reviewed open access monthly journal published by MDPI.

Please visit the Instructions for Authors page before submitting a manuscript. The Article Processing Charge (APC) for publication in this open access journal is 2700 CHF (Swiss Francs). Submitted papers should be well formatted and use good English. Authors may use MDPI's English editing service prior to publication or during author revisions.

Keywords

  • Methanation
  • Carbon dioxide
  • Catalyst
  • Reaction mechanism
  • Deactivation
  • Reactor
  • Photocatalytic
  • Power-to-gas
  • Renewable energy
  • Biogas upgrading
  • Chemical storage

Related Special Issue

Published Papers (7 papers)

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Research

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12 pages, 3587 KiB  
Article
Ru/Al2O3 on Polymer-Derived SiC Foams as Structured Catalysts for CO2 Methanation
by Elisabetta Maria Cepollaro, Stefano Cimino, Luciana Lisi, Mattia Biesuz, Balanand Santhosh and Gian Domenico Sorarù
Catalysts 2022, 12(9), 956; https://0-doi-org.brum.beds.ac.uk/10.3390/catal12090956 - 28 Aug 2022
Cited by 1 | Viewed by 1542
Abstract
The catalytic methanation of CO2 via the strongly exothermic equilibrium Sabatier reaction requires the development of structured catalysts with enhanced mass- and heat-transfer features to limit hot-spot formation, avoid catalyst deactivation, and control process selectivity. In this work, we investigated the use [...] Read more.
The catalytic methanation of CO2 via the strongly exothermic equilibrium Sabatier reaction requires the development of structured catalysts with enhanced mass- and heat-transfer features to limit hot-spot formation, avoid catalyst deactivation, and control process selectivity. In this work, we investigated the use of polymer-derived SiC open-cell foams as structured carriers onto which γ-Al2O3 was applied by either dip-coating or pore-filling methods; eventually, Ru was dispersed by impregnation. The formation of an undesired insulating SiO2 layer on the surface of the SiC struts was prevented by a pyrolysis treatment under an inert atmosphere at temperatures varying from 800 up to 1800 °C. SiC foam substrates and their corresponding structured catalysts were characterized by SEM, XRD, N2 physisorption, and compressive strength measurements, and their CO2 methanation activity was tested at atmospheric pressure in a fixed bed flow reactor operated in the temperature range from 200 to 450 °C. SiC foams obtained at intermediate pyrolysis temperatures (1000–1200 °C) showed good mechanical strength and high compatibility with the Ru/Al2O3 active catalytic overlayer. Full article
(This article belongs to the Special Issue Frontiers in Catalysis for CO2 Methanation)
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13 pages, 4293 KiB  
Article
On the Effect of Cobalt Promotion over Ni/CeO2 Catalyst for CO2 Thermal and Plasma Assisted Methanation
by Golshid Hasrack, Maria Carmen Bacariza, Carlos Henriques and Patrick Da Costa
Catalysts 2022, 12(1), 36; https://0-doi-org.brum.beds.ac.uk/10.3390/catal12010036 - 30 Dec 2021
Cited by 8 | Viewed by 2430
Abstract
In recent years, carbon dioxide hydrogenation leading to synthetic fuels and value-added molecules has been proposed as a promising technology for stabilizing anthropogenic greenhouse gas emissions. Methanation or Sabatier are possible reactions to valorize the CO2. In the present work, thermal [...] Read more.
In recent years, carbon dioxide hydrogenation leading to synthetic fuels and value-added molecules has been proposed as a promising technology for stabilizing anthropogenic greenhouse gas emissions. Methanation or Sabatier are possible reactions to valorize the CO2. In the present work, thermal CO2 methanation and non-thermal plasma (NTP)-assisted CO2 methanation was performed over 15Ni/CeO2 promoted with 1 and 5 wt% of cobalt. The promotion effect of cobalt is proven both for plasma and thermal reaction and can mostly be linked with the basic properties of the materials. Full article
(This article belongs to the Special Issue Frontiers in Catalysis for CO2 Methanation)
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23 pages, 15027 KiB  
Article
The Effects of Ce and W Promoters on the Performance of Alumina-Supported Nickel Catalysts in CO2 Methanation Reaction
by Wojciech Gac, Witold Zawadzki, Magdalena Greluk, Grzegorz Słowik, Marek Rotko and Marcin Kuśmierz
Catalysts 2022, 12(1), 13; https://0-doi-org.brum.beds.ac.uk/10.3390/catal12010013 - 24 Dec 2021
Cited by 3 | Viewed by 3028
Abstract
The influence of Ce and W promoters on the performance of alumina-supported nickel catalysts in the CO2 methanation reaction was investigated. The catalysts were obtained by the co-impregnation method. Nitrogen low-temperature adsorption, temperature-programmed reduction, hydrogen desorption, transmission electron microscopy, X-ray diffraction, and [...] Read more.
The influence of Ce and W promoters on the performance of alumina-supported nickel catalysts in the CO2 methanation reaction was investigated. The catalysts were obtained by the co-impregnation method. Nitrogen low-temperature adsorption, temperature-programmed reduction, hydrogen desorption, transmission electron microscopy, X-ray diffraction, and photoelectron spectroscopy studies were used for catalyst characterization. An introduction of Ce and W promoters (1–5 wt %) led to the decrease in mean Ni crystallite size. Gradual increase in the active surface area was observed only for Ce-promoted catalysts. The increase in CO2 conversion in methanation reaction at low-reaction temperatures carried out over Ce-promoted catalysts was attributed to the increase in the active surface area and changes in the redox properties. The introduction of small amounts of tungsten led to an increase in the activity of catalysts, although a decrease in the active surface area was observed. Quasi in situ XPS studies revealed changes in the oxidation state of tungsten under CO2 methanation reaction conditions, indicating the participation of redox promoter changes in the course of surface reactions, leading to an improvement in the activity of the catalyst. Full article
(This article belongs to the Special Issue Frontiers in Catalysis for CO2 Methanation)
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10 pages, 750 KiB  
Article
A Comparison of the Efficiency of Catalysts Based on Ni, Ni-Co and Ni-Mo in Pressure Pyrolysis of Biomass Leading to Hythane
by Pavel Straka, Olga Bičáková and Tomáš Hlinčík
Catalysts 2021, 11(12), 1480; https://0-doi-org.brum.beds.ac.uk/10.3390/catal11121480 - 03 Dec 2021
Cited by 4 | Viewed by 2079
Abstract
A thermal conversion of biomass to hythane using catalysts was studied. Low-temperature pyrolysis of two different types of biomass was performed in a pressure sealed reactor, and the resulting gas with high contents of CO2 and CO was methanized in a hydrogen [...] Read more.
A thermal conversion of biomass to hythane using catalysts was studied. Low-temperature pyrolysis of two different types of biomass was performed in a pressure sealed reactor, and the resulting gas with high contents of CO2 and CO was methanized in a hydrogen atmosphere at a pressure of 30 bar. As catalysts, Ni/Al2O3, NiCo/Al2O3 and NiMo/Al2O3 were used and their catalytic activity was evaluated. The NiCo/Al2O3 catalyst showed the highest catalytic activity, Ni/Al2O3 had a lower but comparable one, and NiMo/Al2O3 showed the lowest activity. The resulting hythane contained 70 vol.% CH4 and 10 vol.% H2 (with NiCo/Al2O3 catalyst, HHV 29.20 MJ/m3, LHV 26.32 MJ/m3), or 57 vol.% CH4 and 23 vol% H2 (with Ni/Al2O3, HHV 25.92 MJ/m3, LHV 23.21 MJ/m3) or 47 vol.% CH4 and 27 vol.% H2 (with NiMo/Al2O3, HHV 23.23 MJ/m3, LHV 20.76 MJ/m3). It has been found that secondary reactions of volatile biomass products are of great importance for successful pressure pyrolysis. Full article
(This article belongs to the Special Issue Frontiers in Catalysis for CO2 Methanation)
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14 pages, 2870 KiB  
Article
Methanation of CO2 Using MIL-53-Based Catalysts: Ni/MIL-53–Al2O3 versus Ni/MIL-53
by Oana Grad, Gabriela Blanita, Mihaela D. Lazar and Maria Mihet
Catalysts 2021, 11(11), 1412; https://0-doi-org.brum.beds.ac.uk/10.3390/catal11111412 - 21 Nov 2021
Cited by 5 | Viewed by 2423
Abstract
MIL-53 and the MIL-53–Al2O3 composite synthesized by a solvothermal procedure, with water as the only solvent besides CrCl3 and benzene-1,4-dicarboxylic acid (BDC), were used as catalytic supports to obtain the novel MIL-53-based catalysts Ni(10 wt.%)/MIL-53 and Ni(10 wt.%)/MIL-53–Al2 [...] Read more.
MIL-53 and the MIL-53–Al2O3 composite synthesized by a solvothermal procedure, with water as the only solvent besides CrCl3 and benzene-1,4-dicarboxylic acid (BDC), were used as catalytic supports to obtain the novel MIL-53-based catalysts Ni(10 wt.%)/MIL-53 and Ni(10 wt.%)/MIL-53–Al2O3. Ni nanoparticle deposition by an adapted double-solvent method leads to the uniform distribution of metallic particles, both smaller (≤10 nm) and larger ones (10–30 nm). MIL-53–Al2O3 and Ni/MIL-53–Al2O3 show superior thermal stability to MIL-53 and Ni/MIL-53, while MIL-53–Al2O3 samples combine the features of both MIL-53 and alumina in terms of porosity. The investigation of temperature’s effect on the catalytic performance in the methanation process (CO2:H2 = 1:5.2, GHSV = 4650 h−1) revealed that Ni/MIL-53 is more active at temperatures below 300 °C, and Ni/MIL-53–Al2O3 above 300 °C. Both catalysts show maximum CO2 conversion at 350 °C: 75.5% for Ni/MIL-53 (methane selectivity of 93%) and 88.8% for Ni/MIL-53–Al2O3 (methane selectivity of 98%). Stability tests performed at 280 °C prove that Ni/MIL-53–Al2O3 is a possible candidate for the CO2 methanation process due to its high CO2 conversion and CH4 selectivity, corroborated by the preservation of the structure and crystallinity of MIL-53 after prolonged exposure in the reaction medium. Full article
(This article belongs to the Special Issue Frontiers in Catalysis for CO2 Methanation)
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12 pages, 4607 KiB  
Article
CO2 Hydrogenation to Synthetic Natural Gas over Ni, Fe and Co–Based CeO2–Cr2O3
by Chalempol Khajonvittayakul, Vut Tongnan, Suksun Amornraksa, Navadol Laosiripojana, Matthew Hartley and Unalome Wetwatana Hartley
Catalysts 2021, 11(10), 1159; https://0-doi-org.brum.beds.ac.uk/10.3390/catal11101159 - 26 Sep 2021
Cited by 8 | Viewed by 2211
Abstract
CO2 methanation was studied over monometallic catalyst, i.e., Ni, Fe and Co; on CeO2-Cr2O3 support. The catalysts were prepared using one-pot hydrolysis of mixed metal nitrates and ammonium carbonate. Physicochemical properties of the pre- and post-exposure catalysts [...] Read more.
CO2 methanation was studied over monometallic catalyst, i.e., Ni, Fe and Co; on CeO2-Cr2O3 support. The catalysts were prepared using one-pot hydrolysis of mixed metal nitrates and ammonium carbonate. Physicochemical properties of the pre- and post-exposure catalysts were characterized by X-Ray Powder Diffraction (XRD), Hydrogen Temperature Programmed Reduction (H2-TPR), and Field Emission Scanning Electron Microscope (FE-SEM). The screening of three dopants over CeO2-Cr2O3 for CO2 methanation was conducted in a milli-packed bed reactor. Ni-based catalyst was proven to be the most effective catalyst among all. Thus, a group of NiO/CeO2-Cr2O3 catalysts with Ni loading was investigated further. 40 % NiO/CeO2-Cr2O3 exhibited the highest CO2 conversion of 97.67% and CH4 selectivity of 100% at 290 °C. The catalytic stability of NiO/CeO2-Cr2O3 was tested towards the CO2 methanation reaction over 50 h of time-on-stream experiment, showing a good stability in term of catalytic activity. Full article
(This article belongs to the Special Issue Frontiers in Catalysis for CO2 Methanation)
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Review

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26 pages, 4094 KiB  
Review
Review of CO2 Reduction on Supported Metals (Alloys) and Single-Atom Catalysts (SACs) for the Use of Green Hydrogen in Power-to-Gas Concepts
by Ali M. Abdel-Mageed and Sebastian Wohlrab
Catalysts 2022, 12(1), 16; https://0-doi-org.brum.beds.ac.uk/10.3390/catal12010016 - 24 Dec 2021
Cited by 16 | Viewed by 4540
Abstract
The valorization of carbon dioxide by diverting it into useful chemicals through reduction has recently attracted much interest due to the pertinent need to curb increasing global warming, which is mainly due to the huge increase of CO2 emissions from domestic and [...] Read more.
The valorization of carbon dioxide by diverting it into useful chemicals through reduction has recently attracted much interest due to the pertinent need to curb increasing global warming, which is mainly due to the huge increase of CO2 emissions from domestic and industrial activities. This approach would have a double benefit when using the green hydrogen generated from the electrolysis of water with renewable electricity (solar and wind energy). Strategies for the chemical storage of green hydrogen involve the reduction of carbon dioxide to value-added products such as methane, syngas, methanol, and their derivatives. The reduction of CO2 at ambient pressure to methane or carbon monoxide are rather facile processes that can be easily used to store renewable energy or generate an important starting material for chemical industry. While the methanation pathway can benefit from existing infrastructure of natural gas grids, the production of syngas could be also very essential to produce liquid fuels and olefins, which will also be in great demand in the future. In this review, we focus on the recent advances in the thermocatalytic reduction of CO2 at ambient pressure to basically methane and syngas on the surface of supported metal nanoparticles, single-atom catalyst (SACs), and supported bimetallic alloys. Basically, we will concentrate on activity, selectivity, stability during reaction, support effects, metal-support interactions (MSIs), and on some recent approaches to control and switch the CO2 reduction selectivity between methane and syngas. Finally, we will discuss challenges and requirements for the successful introduction of these processes in the cycle of renewable energies. All these aspects are discussed in the frame of sustainable use of renewable energies. Full article
(This article belongs to the Special Issue Frontiers in Catalysis for CO2 Methanation)
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