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Catalytic Reforming and Hydrogen Production: From the Past to the...
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Catalytic Reforming and Hydrogen Production: From the Past to the Future

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

Deadline for manuscript submissions: 30 November 2024 | Viewed by 5148

Special Issue Editors

Dr. Georgios Bampos

E-Mail Website1 Website2
Guest Editor
Department of Chemical Engineering, University of Patras, 26504 Patras, Greece
Interests: catalysis; electrocatalysis; electrochemistry; advanced oxidation processes; hydrocarbon reforming; CO2 reduction
Special Issues, Collections and Topics in MDPI journals
Dr. Paraskevi Panagiotopoulou

E-Mail Website
Guest Editor
School of Environmental Engineering, Technical University of Crete, GR-73100 Chania, Greece
Interests: methane production; catalyst; synthesis gas; hydrogen production; steam reforming; WGS reaction
Special Issues, Collections and Topics in MDPI journals
Dr. Eleni A. Kyriakidou

E-Mail Website
Guest Editor
Department of Chemical and Biological Engineering, University at Buffalo, The State University of New York, Buffalo, NY 14260, USA
Interests: heterogeneous catalysis; nanoparticle synthesis; surface science; catalysts; environmental processes

Special Issue Information

Dear Colleagues,

The Special Issue is dedicated to the exploration of catalytic reforming and hydrogen production, delving into a journey starting in the past of these processes and ending in their future applications. The catalytic reforming of light hydrocarbons stands out as a prominent technique for generating valuable products like synthesis gas. Syngas, a crucial intermediary substance in the creation of hydrogen, ammonia, methanol, and synthetic hydrocarbon fuels, holds significant potential for fostering a cleaner, more sustainable energy environment. Furthermore, through advancements in catalyst development, reactor designs, and process optimization strategies, hydrogen has emerged as a pivotal player in the global energy shift towards a more efficient and sustainable hydrogen economy.

This Special Issue aims to showcase the most recent research findings in heterogeneous catalysis concerning catalytic reforming and hydrogen production, assuming a future where clean energy takes center stage. We invite submissions in the form of original research papers or reviews that reflect the state of the art of this research area. Topics of interest include, but are not limited to, the following:

  • Methane conversion.
  • Dry reforming.
  • CO2 methanation.
  • Hydrogen production processes.
  • Water–gas shift (WGS) reaction.
  • Production of syngas.
  • Fischer–Tropsch synthesis.
  • Fuel cells.

Dr. Georgios Bampos
Dr. Paraskevi Panagiotopoulou
Dr. Eleni A. Kyriakidou
Guest Editors

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 2200 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

  • syngas
  • hydrogen production
  • steam reforming
  • CO2 methanation
  • water gas shift (WGS) reaction
  • fuels
  • clean energy
  • hydrocarbons to fuels
  • fuel cells

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Published Papers (6 papers)

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Research

16 pages, 7807 KiB  
Article
Aqueous Phase Reforming by Platinum Catalysts: Effect of Particle Size and Carbon Support
by Xuan Trung Nguyen, Ella Kitching, Thomas Slater, Emanuela Pitzalis, Jonathan Filippi, Werner Oberhauser and Claudio Evangelisti
Catalysts 2024, 14(11), 798; https://doi.org/10.3390/catal14110798 - 7 Nov 2024
Viewed by 597
Abstract
Aqueous phase reforming (APR) is a promising method for producing hydrogen from biomass-derived feedstocks. In this study, carbon-supported Pt catalysts containing particles of different sizes (below 3 nm) were deposited on different commercially available carbons (i.e., Vulcan XC72 and Ketjenblack EC-600JD) using the [...] Read more.
Aqueous phase reforming (APR) is a promising method for producing hydrogen from biomass-derived feedstocks. In this study, carbon-supported Pt catalysts containing particles of different sizes (below 3 nm) were deposited on different commercially available carbons (i.e., Vulcan XC72 and Ketjenblack EC-600JD) using the metal vapor synthesis approach, and their catalytic efficiency and stability were evaluated in the aqueous phase reforming of ethylene glycol, the simplest polyol containing both C–C and C–O bonds. High-surface-area carbon supports were found to stabilize Pt nanoparticles with a mean diameter of 1.5 nm, preventing metal sintering. In contrast, Pt single atoms and clusters (below 0.5 nm) were not stable under the reaction conditions, contributing minimally to catalytic activity and promoting particle growth. The most effective catalyst PtA/CK, containing a mean Pt NP size of 1.5 nm and highly dispersed on Ketjenblack carbon, demonstrated high hydrogen site time yield (8.92 min−1 at 220 °C) and high stability under both high-temperature treatment conditions and over several recycling runs. The catalyst was also successfully applied to the APR of polyethylene terephthalate (PET), showing potential for hydrogen production from plastic waste. Full article
(This article belongs to the Special Issue Catalytic Reforming and Hydrogen Production: From the Past to the Future)
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12 pages, 8618 KiB  
Article
Hydrogen and CO Over-Equilibria in Catalytic Reactions of Methane Reforming
by Vitaliy R. Trishch, Mykhailo O. Vilboi, Gregory S. Yablonsky and Dmytro O. Kovaliuk
Catalysts 2024, 14(11), 773; https://doi.org/10.3390/catal14110773 - 31 Oct 2024
Viewed by 449
Abstract
Hydrogen and carbon monoxide over-equilibria have been found computationally in kinetic dependencies of methane-reforming catalytic reactions (steam and dry reforming) using the conditions of the conservatively perturbed equilibrium (CPE) phenomenon, i.e., at the initial equilibrium concentration of hydrogen or carbon monoxide. The influence [...] Read more.
Hydrogen and carbon monoxide over-equilibria have been found computationally in kinetic dependencies of methane-reforming catalytic reactions (steam and dry reforming) using the conditions of the conservatively perturbed equilibrium (CPE) phenomenon, i.e., at the initial equilibrium concentration of hydrogen or carbon monoxide. The influence of the pressure, temperature, flow rate and composition of the initial mixture on the position of the CPE point (the extremum point) was investigated over a wide domain of parameters. The CPE phenomenon significantly increases the product concentration (H2 and CO) at the reactor length, which is significantly less than the reactor length required to reach equilibrium. The CPE point is interpreted as the “turning point” in kinetic behaviour. Recommendations on temperature and pressure regimes are different from the traditional ones related to Le Chatelier’s law. The obtained results provide valuable information on optimal reaction conditions for complex reversible chemical transformations, offering potential applications in chemical engineering processes. Full article
(This article belongs to the Special Issue Catalytic Reforming and Hydrogen Production: From the Past to the Future)
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18 pages, 4765 KiB  
Article
Kinetic Characterization of Pt/Al2O3 Catalyst for Hydrogen Production via Methanol Aqueous-Phase Reforming
by José Sousa, Paranjeet Lakhtaria, Paulo Ribeirinha, Werneri Huhtinen, Johan Tallgren and Adélio Mendes
Catalysts 2024, 14(10), 741; https://doi.org/10.3390/catal14100741 - 21 Oct 2024
Viewed by 749
Abstract
Compared to steam reforming, methanol aqueous-phase reforming (APR) converts methanol to hydrogen and carbon dioxide at lower temperatures, but also displays lower conversion rates. Herein, methanol APR is studied over the active Pt/Al2O3 catalyst under different operating conditions. Studies were [...] Read more.
Compared to steam reforming, methanol aqueous-phase reforming (APR) converts methanol to hydrogen and carbon dioxide at lower temperatures, but also displays lower conversion rates. Herein, methanol APR is studied over the active Pt/Al2O3 catalyst under different operating conditions. Studies were conducted at different temperatures, pressures, methanol mass fractions, and residence times. APR performance was evaluated in terms of methanol conversion, hydrogen production rate, hydrogen selectivity, and by-product formation. The results revealed that an increase in operating pressure and methanol mass fraction had an adverse effect on the APR performance. Conversely, it was found that hydrogen selectivity was unaffected by the operating pressure and residence time for the methanol feed mass fraction of 5%. For the methanol feed mass fraction of 55%, hydrogen selectivity was improved by operating pressure and residence time. The alumina support phase change to boehmite as well as sintering and leaching of the catalytic particles were observed during catalyst stability experiments. Additionally, a comparison between methanol steam reforming (MSR) and APR was also performed. Full article
(This article belongs to the Special Issue Catalytic Reforming and Hydrogen Production: From the Past to the Future)
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20 pages, 5958 KiB  
Article
Dry Reforming of Methane (DRM) over Hydrotalcite-Based Ni-Ga/(Mg, Al)Ox Catalysts: Tailoring Ga Content for Improved Stability
by Ahmed Y. Elnour, Ahmed E. Abasaeed, Anis H. Fakeeha, Ahmed A. Ibrahim, Salwa B. Alreshaidan and Ahmed S. Al-Fatesh
Catalysts 2024, 14(10), 721; https://doi.org/10.3390/catal14100721 - 16 Oct 2024
Viewed by 739
Abstract
Dry reforming of methane (DRM) is a promising way to convert methane and carbon dioxide into syngas, which can be further utilized to synthesize value-added chemicals. One of the main challenges for the DRM process is finding catalysts that are highly active and [...] Read more.
Dry reforming of methane (DRM) is a promising way to convert methane and carbon dioxide into syngas, which can be further utilized to synthesize value-added chemicals. One of the main challenges for the DRM process is finding catalysts that are highly active and stable. This study explores the potential use of Ni-based catalysts modified by Ga. Different Ni-Ga/(Mg, Al)Ox catalysts, with various Ga/Ni molar ratios (0, 0.1, 0.3, 0.5, and 1), were synthesized by the co-precipitation method. The catalysts were tested for the DRM reaction to evaluate their activity and stability. The Ni/(Mg, Al)Ox and its Ga-modified Ni-Ga/(Mg, Al)Ox were characterized by N2 adsorption–desorption, Fourier Transform Infrared Spectroscopy (FTIR), H2-temperature-programmed reduction (TPR), X-ray diffraction (XRD), thermogravimetric analysis (TGA) and Raman techniques. The test of catalytic activity, at 700 °C, 1 atm, GHSV of 42,000 mL/h/g, and a CH4: CO2 ratio of 1, revealed that Ga incorporation effectively enhanced the catalyst stability. Particularly, the Ni-Ga/(Mg, Al)Ox catalyst with Ga/Ni ratio of 0.3 exhibited the best catalytic performance, with CH4 and CO2 conversions of 66% and 74%, respectively, and an H2/CO ratio of 0.92. Furthermore, the CH4 and CO2 conversions increased from 34% and 46%, respectively, when testing at 600 °C, to 94% and 96% when the catalytic activity was operated at 850 °C. The best catalyst’s 20 h stream performance demonstrated its great stability. DFT analysis revealed an alteration in the electronic properties of nickel upon Ga incorporation, the d-band center of the Ga modified catalyst (Ga/Ni ratio of 0.3) shifted closer to the Fermi level, and a charge transfer from Ga to Ni atoms was observed. This research provides valuable insights into the development of Ga-modified catalysts and emphasizes their potential for efficient conversion of greenhouse gases into syngas. Full article
(This article belongs to the Special Issue Catalytic Reforming and Hydrogen Production: From the Past to the Future)
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18 pages, 2811 KiB  
Article
Are Rh Catalysts a Suitable Choice for Bio-Oil Reforming? The Case of a Commercial Rh Catalyst in the Combined H2O and CO2 Reforming of Bio-Oil
by José Valecillos, Leire Landa, Gorka Elordi, Aingeru Remiro, Javier Bilbao and Ana Guadalupe Gayubo
Catalysts 2024, 14(9), 571; https://doi.org/10.3390/catal14090571 - 29 Aug 2024
Viewed by 638
Abstract
Bio-oil combined steam/dry reforming (CSDR) with H2O and CO2 as reactants is an attractive route for the joint valorization of CO2 and biomass towards the sustainable production of syngas (H2 + CO). The technological development of the process [...] Read more.
Bio-oil combined steam/dry reforming (CSDR) with H2O and CO2 as reactants is an attractive route for the joint valorization of CO2 and biomass towards the sustainable production of syngas (H2 + CO). The technological development of the process requires the use of an active and stable catalyst, but also special attention should be paid to its regeneration capacity due to the unavoidable and quite rapid catalyst deactivation in the reforming of bio-oil. In this work, a commercial Rh/ZDC (zirconium-doped ceria) catalyst was tested for reaction–regeneration cycles in the bio-oil CSDR in a fluidized bed reactor, which is beneficial for attaining an isothermal operation and, moreover, minimizes catalyst deactivation by coke deposition compared to a fixed-bed reactor. The fresh, spent, and regenerated catalysts were characterized using either N2 physisorption, H2-TPR, TPO, SEM, TEM, or XRD. The Rh/ZDC catalyst is initially highly active for the syngas production (yield of 77% and H2/CO ratio of 1.2) and for valorizing CO2 (conversion of 22%) at 700 °C, with space time of 0.125 gcatalyst h (goxygenates)−1 and CO2/H2O/C ratio of 0.6/0.5/1. The catalyst activity evolves in different periods that evidence a selective deactivation of the catalyst for the reforming reactions of the different compounds, with the CH4 reforming reactions (with both steam and CO2) being more rapidly affected by catalyst deactivation than the reforming of hydrocarbons or oxygenates. After regeneration, the catalyst’s textural properties are not completely restored and there is a change in the Rh–support interaction that irreversibly deactivates the catalyst for the CH4 reforming reactions (both SR and DR). As a result, the coke formed over the regenerated catalyst is different from that over the fresh catalyst, being an amorphous mass (of probably turbostractic nature) that encapsulates the catalyst and causes rapid deactivation. Full article
(This article belongs to the Special Issue Catalytic Reforming and Hydrogen Production: From the Past to the Future)
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19 pages, 5418 KiB  
Article
Ni-Ag Catalysts for Hydrogen Production through Dry Reforming of Methane: Characterization and Performance Evaluation
by Hayat Henni, Rafik Benrabaa, Pascal Roussel and Axel Löfberg
Catalysts 2024, 14(7), 400; https://doi.org/10.3390/catal14070400 - 25 Jun 2024
Cited by 1 | Viewed by 1171
Abstract
To investigate the influence of Ag and the loading of Ni species, Ni-Ag type catalysts were synthesized with varying Ni/Ag ratios (1, 1.5 and 2) using the coprecipitation method. The catalysts were extensively characterized using various techniques such as TG-DSC-SM, XRD, ICP, BET, [...] Read more.
To investigate the influence of Ag and the loading of Ni species, Ni-Ag type catalysts were synthesized with varying Ni/Ag ratios (1, 1.5 and 2) using the coprecipitation method. The catalysts were extensively characterized using various techniques such as TG-DSC-SM, XRD, ICP, BET, SEM-EDX and TPR and subsequently tested in the CH4/CO2 reaction without any pretreatment. Regardless of the ratio employed, a phase mixture containing NiO and Ag was observed after calcination under air between 600 °C and 1200 °C. SEM analysis confirmed the presence of a close interface between Ag and NiO. The specific surface area was found to be significantly higher for the catalyst with lower Ni content (R = 1). TPR analysis demonstrated that the inclusion of Ag facilitated the reduction of Ni at lower temperatures. XRD analyses of the spent catalyst confirmed catalyst reduction during the reaction. Among the samples, a catalyst with Ni/Ag = 1 exhibited superior catalytic activity without any pretreatment under a reduction atmosphere, in which case the conversions of methane and CO2 at 650 °C amounted to 38 and 45 mol%, respectively, with H2/CO = 0.7 and 71 mol% of H2. The presence of Ag species enhances the stability of the Ni catalyst and improves catalytic performance in the dry reforming of methane. Full article
(This article belongs to the Special Issue Catalytic Reforming and Hydrogen Production: From the Past to the Future)
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