Special Issue "Catalytic Steam Reforming"

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

Deadline for manuscript submissions: closed (31 December 2020) | Viewed by 9210

Special Issue Editor

Dr. Dong Ju Moon
E-Mail Website
Guest Editor
Korea Institute of Science and Technology, Seoul, Republic of Korea KIST-School, UST, Seoul, Korea
Interests: carbon neutralization; catalytic reforming; clean fuel; hydrogen station; syngas synthesis
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Special Issue Information

Dear Colleagues,

Hydrogen is known as an alternative viable, clean fuel, and the implementation of hydrogen will possess a significant role as a key energy carrier in balancing both energy supply and demand. At the moment, approximately 96% of hydrogen is produced from fossil fuels. Steam reforming (SR) is the most economical method. At the industrial scale, 48% of total hydrogen is produced from the SR of natural gas, 30% from oil, 18% from coal, and only 4% from water electrolysis. The conventional SR of natural gas includes two main steps: endothermic SR reaction at a high temperature (1000∼1300 K) and exothermic water gas shift (WGS) reaction at a lower temperature (500∼700 K). For the development of small-scale reformers, on-site hydrogen stations, and large-scale reformers, it is also highly essential to develop a compact reactor with proper catalytic activity and reliable durability to avoid the sintering of active metal and coke formation.

This Special Issue of Catalysts will mainly include the development of catalysts, reactor and process designs with CFD modeling and process optimization to enhance the performance of the SR for the application in small-scale fuel processors, hydrogen stations, large-scale reformers, and commercial hydrogen plants. The primary purpose is the development of novel methods for steam reforming of natural gas, other hydrocarbons, and liquid fuels for the application in the compact hydrogen station.

Dr. Dong Ju Moon
Guest Editor

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Keywords

  • steam reforming
  • water gas shift reaction
  • structured catalysts
  • CDF modeling
  • reactor deign
  • reforming process design
  • small-scale reformer
  • hydrogen station
  • large-scale and commercial reformer

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Published Papers (7 papers)

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Research

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Article
Upgrading of Bio-Syngas via Steam-CO2 Reforming Using Rh/Alumina Monolith Catalysts
Catalysts 2021, 11(2), 180; https://doi.org/10.3390/catal11020180 - 28 Jan 2021
Cited by 2 | Viewed by 834
Abstract
Steam-CO2 reforming of biomass derived synthesis gas (bio-syngas) was investigated with regard to the steam concentration in the feed using Rh-loaded alumina foam monolith catalysts, which was also accompanied by thermodynamic equilibrium calculation. With 40 vol % steam addition, steam methane reforming [...] Read more.
Steam-CO2 reforming of biomass derived synthesis gas (bio-syngas) was investigated with regard to the steam concentration in the feed using Rh-loaded alumina foam monolith catalysts, which was also accompanied by thermodynamic equilibrium calculation. With 40 vol % steam addition, steam methane reforming and water gas shift reaction were prevailed at the temperature below 640 °C, above which methane dry reforming and reverse-water gas shift reaction were intensified. Substantial change of activation energy based on the methane conversion was observed at 640 °C, where the reaction seemed to be shifted from the kinetic controlled region to the mass transfer controlled region. At the reduced steam of 20 vol %, the increase in the gas velocity led to the increase in the contribution of steam reforming. Comparing to the absence of steam, the addition of steam (40 vol %) resulted in the increase in the production of H2 and CO2, which in turn increased the H2/CO ratio by 95% and decreased the CO/CO2 ratio by 60%. Rh-loaded alumina monolith was revealed to have a good stability in upgrading of the raw bio-syngas. Full article
(This article belongs to the Special Issue Catalytic Steam Reforming)
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Article
Preparation and Characterization of Ni/ZrTiAlOx Catalyst via Sol-Gel and Impregnation Methods for Low Temperature Dry Reforming of Methane
Catalysts 2020, 10(11), 1335; https://doi.org/10.3390/catal10111335 - 17 Nov 2020
Cited by 2 | Viewed by 1030
Abstract
Recently, the dry reforming of methane (DRM) has received much attention as a conversion technology of greenhouse gases. Ni-based catalysts supported on ternary metal oxide composite (ZrTiAlOx) were prepared to improve the coke resistance properties in the DRM (CH4:CO [...] Read more.
Recently, the dry reforming of methane (DRM) has received much attention as a conversion technology of greenhouse gases. Ni-based catalysts supported on ternary metal oxide composite (ZrTiAlOx) were prepared to improve the coke resistance properties in the DRM (CH4:CO2 = 1) at low temperature. The ZrTiAlOx supports with different ratios of Zr/Ti were prepared through the modified Pechini sol-gel method, and then the Ni was impregnated on the synthesized support via the incipient wetness impregnation method. Considering the Zr/Ti ratios, different catalytic activity and durability in the DRM were identified. The Ni/ZrTiAlOx catalyst with Zr/Ti of 2 exhibited enhanced coke inhibition property compared to the others at low temperature DRM for 50 h. The catalysts with a high Zr/Ti ratio under the same condition were rapidly deactivated, while the catalyst with a low Zr/Ti ratio showed deficient activity. It was found from temperature-programmed surface reactions (TPSR) and DRIFTS (Diffuse Reflectance Infrared Fourier Transform Spectroscopy) analysis that the addition of Ti has led in to higher catalytic stability at Zr/Ti = 2, which could be as a result of oxygen vacancies generated by the ternary metal oxides. Ni/ZrTiAlOx catalyst with ratio of Zr/Ti = 2 showed high stability and good catalytic activity towards DRM for the production of syngas. Full article
(This article belongs to the Special Issue Catalytic Steam Reforming)
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Article
CeZrOx Promoted Water-Gas Shift Reaction under Steam–Methane Reforming Conditions on Ni-HTASO5
Catalysts 2020, 10(10), 1110; https://doi.org/10.3390/catal10101110 - 25 Sep 2020
Cited by 1 | Viewed by 832
Abstract
Ni-based catalysts (Ni-γ-Al2O3, Ni-HTASO5 and Ni-CeZrOx) were prepared by impregnation method and characterized by BET, AAS, XRD, H2-TPR, CO-TPD, NH3-TPD, XPS, TG-DSC-MS and Raman spectroscopies. Using CeZrOx-modified Al2O3 [...] Read more.
Ni-based catalysts (Ni-γ-Al2O3, Ni-HTASO5 and Ni-CeZrOx) were prepared by impregnation method and characterized by BET, AAS, XRD, H2-TPR, CO-TPD, NH3-TPD, XPS, TG-DSC-MS and Raman spectroscopies. Using CeZrOx-modified Al2O3 (HTASO5) as support, the catalyst exhibited good catalytic performance (TOFCH4 = 8.0 × 10−2 s−1, TOFH2 = 10.5 × 10−2 s−1) and carbon resistance for steam-methane reforming (SMR) reaction. Moreover, CeZrOx was able to enhance water-gas shift (WGS) reaction for more hydrogen production. It was found that the addition of CeZrOx could increase the content of active nickel precursor on the surface of the catalyst, which was beneficial to the decomposition of water and methane on Ni-HTASO5. Furthermore, Ni-HTASO5 could decrease the strong acid sites of the catalyst, which would not only contribute to the formation of low graphited carbon, but also decrease the amount of carbon deposition. Full article
(This article belongs to the Special Issue Catalytic Steam Reforming)
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Article
Mechanistic Insights for Dry Reforming of Methane on Cu/Ni Bimetallic Catalysts: DFT-Assisted Microkinetic Analysis for Coke Resistance
Catalysts 2020, 10(9), 1043; https://doi.org/10.3390/catal10091043 - 10 Sep 2020
Cited by 21 | Viewed by 2003
Abstract
Density functional theory (DFT) calculations have been utilized to evaluate the complete reaction mechanism of methane dry reforming (DRM) over Ni2Cu (111) bimetallic catalyst. The detailed catalytic cycle on Ni2Cu (111) catalyst demonstrated superior coke resistance compared to pure [...] Read more.
Density functional theory (DFT) calculations have been utilized to evaluate the complete reaction mechanism of methane dry reforming (DRM) over Ni2Cu (111) bimetallic catalyst. The detailed catalytic cycle on Ni2Cu (111) catalyst demonstrated superior coke resistance compared to pure Ni (111) and Ni2Fe (111) reported in the literature. Doping Cu in the Ni–Ni network enhanced the competitive CH oxidation by both atomic O and OH species with the latter having only 0.02 eV higher than the 1.06 eV energy barrier required for CH oxidation by atomic O. Among the C/CH oxidation pathways, C* + O* → CO (g) was the most favorable with an energy barrier of 0.72 eV. This was almost half of the energy barrier required for the rate-limiting step of CH decomposition (1.40 eV) and indicated enhanced coke deposition removal. Finally, we investigated the effect of temperature (800~1000 K) on the carbon deposition and elimination mechanism over Ni2Cu (111) catalyst. Under those realistic DRM conditions, the calculations showed a periodic cycle of simultaneous carbon deposition and elimination resulting in improved catalyst stability. Full article
(This article belongs to the Special Issue Catalytic Steam Reforming)
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Article
Synergy Effects of Cobalt Oxides on Ni/Co-Embedded Al2O3 for Hydrogen-Rich Syngas Production by Steam Reforming of Propane
Catalysts 2020, 10(4), 461; https://doi.org/10.3390/catal10040461 - 24 Apr 2020
Cited by 6 | Viewed by 1109
Abstract
The synergetic effects of Co oxides on the Ni/CoAl (NCA) catalysts were observed at an optimal molar ratio of Al/Co = 2 (NCA(2)) due to the partial formations of thermally stable spinel CoAl2O4 phases for the steam reforming of propane [...] Read more.
The synergetic effects of Co oxides on the Ni/CoAl (NCA) catalysts were observed at an optimal molar ratio of Al/Co = 2 (NCA(2)) due to the partial formations of thermally stable spinel CoAl2O4 phases for the steam reforming of propane (SRP). The optimal content of the spinel CoAl2O4 phases on the NCA(2) was responsible for the formation of the relatively active oxophilic metallic Co nanoparticles with a smaller amount of less active NiAl2O4 on the surfaces by preserving the relative amount of metallic Co of 68% and 52% in the reduced and used catalysts, which enhanced the catalytic activity and stability with the largest specific rate of 1.37 C3H8/(Ni + Co)h−1 among the tested NCA catalysts. The larger or smaller amounts of Co metal on the less active NCA mainly caused the preferential formation of larger aggregated Ni nanoparticles ~16 nm in size due to their weaker interactions, or induced the smaller formations of active metal phases by selectively forming the spinel NiAl2O4 phases with ~60% in the NCA(4), resulting in a fast deactivation. Full article
(This article belongs to the Special Issue Catalytic Steam Reforming)
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Article
Density Functional Theory Based Micro- and Macro-Kinetic Studies of Ni-Catalyzed Methanol Steam Reforming
Catalysts 2020, 10(3), 349; https://doi.org/10.3390/catal10030349 - 20 Mar 2020
Cited by 4 | Viewed by 1277
Abstract
The intrinsic mechanism of Ni-catalyzed methanol steam reforming (MSR) is examined by considering 54 elementary reaction steps involved in MSR over Ni(111). Density functional theory computations and transition state theory analyses are performed on the elementary reaction network. A microkinetic model is constructed [...] Read more.
The intrinsic mechanism of Ni-catalyzed methanol steam reforming (MSR) is examined by considering 54 elementary reaction steps involved in MSR over Ni(111). Density functional theory computations and transition state theory analyses are performed on the elementary reaction network. A microkinetic model is constructed by combining the quantum chemical results with a continuous stirring tank reactor model. MSR rates deduced from the microkinetic model agree with the available experimental data. The microkinetic model is used to identify the main reaction pathway, the rate determining step, and the coverages of surface species. An analytical expression of MSR rate is derived based on the dominant reaction pathway and the coverages of surface species. The analytical rate equation is easy to use and should be very helpful for the design and optimization of the operating conditions of MSR. Full article
(This article belongs to the Special Issue Catalytic Steam Reforming)
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Review

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Review
A Review on Catalysts Development for Steam Reforming of Biodiesel Derived Glycerol; Promoters and Supports
Catalysts 2020, 10(8), 910; https://doi.org/10.3390/catal10080910 - 10 Aug 2020
Cited by 18 | Viewed by 1573
Abstract
In the last decades, environmental crises and increasing energy demand have motivated researchers to investigate the practical techniques for the production of clean fuels through renewable energy resources. It is essential to develop technologies to utilize glycerol as a byproduct derived from biodiesel. [...] Read more.
In the last decades, environmental crises and increasing energy demand have motivated researchers to investigate the practical techniques for the production of clean fuels through renewable energy resources. It is essential to develop technologies to utilize glycerol as a byproduct derived from biodiesel. Glycerol is known as a sustainable and clean source of energy, which can be an alternative resource for the production of value-added chemicals and hydrogen. The hydrogen production via steam reforming (SR) of glycerol using Ni-based catalysts is one of the promising approaches for the entry of the hydrogen economy. The purpose of this review paper is to highlight the recent trends in hydrogen production over Ni-based catalysts using the SR of glycerol. The intrinsic ability of Ni to disperse easily over variable supports makes it a more viable active phase for the SR catalysts. The optimal reaction conditions have been indicated as 650–900 °C, 1 bar, and 15 wt% Ni in catalysts for high glycerol conversion. In this review paper, the effects of various supports, different promoters (K, Ca, Sr, Ce, La, Cr, Fe), and process conditions on the catalytic performance have been summarized and discussed to provide a better comparison for the future works. It was found that Ce, Mg, and La have a significant effect on catalytic performance as promoters. Moreover, SR of glycerol over hydrotalcite and perovskite-based catalysts have been reviewed as they suggest high catalytic performance in SR of glycerol with improved thermal stability and coke resistance. More specifically, the Ni/LaNi0.9Cu0.1O3 synthesized using perovskite-type supports has shown high glycerol conversion and sufficient hydrogen selectivity at low temperatures. On the other hand, hydrotalcite-like catalysts have shown higher catalytic stability due to high thermal stability and low coke formation. It is vital to notice that the primary concern is developing a high-performance catalyst to utilize crude glycerol efficiently. Full article
(This article belongs to the Special Issue Catalytic Steam Reforming)
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