Catalytic Reforming for Syngas and H2 Productions

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

Deadline for manuscript submissions: closed (31 August 2022) | Viewed by 21006

Special Issue Editors


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Guest Editor
Department of Mechanical Engineering, National Chung Hsing University, Taichung 40227, Taiwan
Interests: catalytic syngas/hydrogen production; chemical-looping reforming for syngas/hydrogen production, CO/CO2 methanation, and water-gas shift reaction

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Guest Editor
Department of Aeronautics and Astronautics, National Cheng Kung University, Tainan 701, Taiwan
Interests: bioenergy; hydrogen energy; clean energy; thermoelectric generation; environmental engineering; AI & machine leaning for energy
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Special Issue Information

Dear Colleagues,

Syngas is an important intermediate material for the production of hydrogen, ammonia, methanol, and synthetic hydrocarbon fuels. Syngas can be produced effectively via catalytic reactions from many sources, including natural gas, coal, biomass, or any hydrocarbon feedstock. Due to the advantages of non-toxic, clean, high heating value, and versatile applications, hydrogen plays a crucial role in the economy and it attracts significant interest from scientific researchers. In general, hydrogen can be obtained from the catalytically produced syngas via purification or separation techniques.  

This Special Issue will provide insights into the challenges of catalytic syngas and hydrogen production. These challenges include cost-effective catalyst design, catalyst deactivation resistance, energy consumption reduction, CO2 emission reduction, feedstock pretreatment, and hydrogen separation. Submissions are welcome in the form of original research papers or short reviews that reflect the state-of-the-art of this research area.

Prof. Dr. Rei-Yu Chein
Prof. Dr. Wei-Hsin Chen
Guest Editors

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Keywords

  • Syngas
  • hydrogen
  • catalytic reactions
  • catalyst deactivation
  • energy consumption
  • CO2 emission
  • feedstock pretreatment
  • hydrogen separation.

Published Papers (8 papers)

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Research

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19 pages, 12353 KiB  
Article
Na Promotion of Pt/m-ZrO2 Catalysts for the Steam Reforming of Formaldehyde
by Michela Martinelli, Elijah S. Garcia, Zahra Rajabi, Caleb D. Watson, A. Jeremy Kropf, Donald C. Cronauer and Gary Jacobs
Catalysts 2022, 12(11), 1294; https://doi.org/10.3390/catal12111294 - 22 Oct 2022
Cited by 3 | Viewed by 1513
Abstract
The decomposition selectivity of formaldehyde during steam reforming was explored using unpromoted and sodium promoted Pt/m-ZrO2 catalysts, and the Na content was varied (0.5%Na, 1%Na, 1.8%Na, 2.5%Na, and 5%Na). In situ DRIFTS experiments during temperature programmed reaction in flowing H2O [...] Read more.
The decomposition selectivity of formaldehyde during steam reforming was explored using unpromoted and sodium promoted Pt/m-ZrO2 catalysts, and the Na content was varied (0.5%Na, 1%Na, 1.8%Na, 2.5%Na, and 5%Na). In situ DRIFTS experiments during temperature programmed reaction in flowing H2O revealed that formaldehyde is adsorbed at reduced defect sites on zirconia, where it is converted to formate species through the addition of labile bridging OH species. Formate species achieve a maximum intensity in the range of 125–175 °C, where only slight changes in intensity are observed. Above this temperature, the formate decomposition reactivity strongly depends on the Na loading, with the optimum loadings being 1.8%Na and 2.5%Na. CO2 temperature programmed desorption results, as well as a greater splitting observed between the formate νasym(OCO) and νsym(OCO) bands in infrared spectroscopy, indicate greater basicity is induced by the presence of Na. This strengthens the interaction between the formate -CO2 functional group and the catalyst surface, weakening the formate C-H bond. A shift in the ν(CH) band of formate to lower wavenumbers was observed by addition of Na, especially at 1.8%Na and higher loadings. This results in enhanced decarboxylation and dehydrogenation of formate, as observed in in situ DRIFTS, temperature-programmed reaction/mass spectrometry experiments of the steam reforming of formaldehyde, and fixed bed reaction tests. For example, 2.5%Na addition of 2.5% increased the CO2 selectivity from 83.5% to 99.5% and the catalysts achieved higher stable conversion at lower temperature than NiO catalysts reported in the open literature. At 5%Na loading, Pt sites were severely blocked, hindering H-transfer. Full article
(This article belongs to the Special Issue Catalytic Reforming for Syngas and H2 Productions)
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13 pages, 4891 KiB  
Article
Synthesis of Mesoporous Cu-Ni/Al2O4 Catalyst for Hydrogen Production via Hydrothermal Reconstruction Route
by Kai-Jhei Lin, Yi-Kai Chih, Wei-Hsin Chen, Hsin-Kai Huang, Hong-Ping Lin and Chun-Han Hsu
Catalysts 2022, 12(1), 32; https://doi.org/10.3390/catal12010032 - 28 Dec 2021
Cited by 3 | Viewed by 1998
Abstract
Mesoporous Cu-Ni/Al2O4 catalyst of high surface area (176 m2g−1) is synthesized through a simple hydrothermal reconstruction process by using low-cost activated alumina as the aluminate source without organic templates. The desired mesoporous structure of the catalyst [...] Read more.
Mesoporous Cu-Ni/Al2O4 catalyst of high surface area (176 m2g−1) is synthesized through a simple hydrothermal reconstruction process by using low-cost activated alumina as the aluminate source without organic templates. The desired mesoporous structure of the catalyst is formed by the addition of Cu2+ and Ni2+ metal ions in the gel solution of the activated alumina followed by hydrothermal treatment at 70 °C and calcination at temperatures in the range of 600 to 800 °C. To consider the environmental concern, we found the concentration of the Cu2+ and Ni2+ ion in the residual filtrate is less than 0.1 ppm which satisfies the effluent standard in Taiwan (<1.0 ppm). The effects of the pH value, hydrothermal treatment time, and calcination temperature on the structure, morphology and surface area of the synthesized Cu-Ni/Al2O4 composites are investigated as well. In addition, the Cu-Ni/Al2O4 catalyst synthesized at pH 9.0 with a hydrothermal treatment time of 24 h and a calcination temperature of 600 °C is used for hydrogen production via the partial oxidation of methanol. The conversion efficiency is found to be >99% at a reaction temperature of around 315 °C, while the H2 yield is 1.99 mol H2/mol MeOH. The catalyst retains its original structure and surface area following the reaction process, and is thus inferred to have a good stability. Overall, the hydrothermal reconstruction route described herein is facile and easily extendable to the preparation of other mesoporous metal-alumina materials for catalyst applications. Full article
(This article belongs to the Special Issue Catalytic Reforming for Syngas and H2 Productions)
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21 pages, 3481 KiB  
Article
Autothermal Reforming of Acetic Acid to Hydrogen and Syngas on Ni and Rh Catalysts
by Lifita N. Tande, Erik Resendiz-Mora, Valerie Dupont and Martyn V. Twigg
Catalysts 2021, 11(12), 1504; https://doi.org/10.3390/catal11121504 - 10 Dec 2021
Cited by 6 | Viewed by 2600
Abstract
The autothermal reforming (ATR) of acetic acid (HAc) as a model bio-oil compound is examined via bench scale experiments and equilibrium modelling to produce hydrogen and syngas. This study compares the performance of nickel (Ni-Al, Ni-CaAl) vs. rhodium (Rh-Al) for particulate packed bed [...] Read more.
The autothermal reforming (ATR) of acetic acid (HAc) as a model bio-oil compound is examined via bench scale experiments and equilibrium modelling to produce hydrogen and syngas. This study compares the performance of nickel (Ni-Al, Ni-CaAl) vs. rhodium (Rh-Al) for particulate packed bed (PPB), and of Rh-Al in PPB vs. Rh with and without Ceria for honeycomb monolith (‘M’) catalysts (R-M and RC-M). All PPB and M catalysts used Al2O3 as main support or washcoat, and when not pre-reduced, exhibited good performance with more than 90% of the HAc converted to C1-gases. The maximum H2 yield (6.5 wt.% of feed HAc) was obtained with both the Rh-Al and Ni-CaAl catalysts used in PPB, compared to the equilibrium limit of 7.2 wt.%, although carbon deposition from Ni-CaAl at 13.9 mg gcat−1 h−1 was significantly larger than Rh-Al’s (5.5 mg gcat−1 h−1); close to maximum H2 yields of 6.2 and 6.3 wt.% were obtained for R-M and RC-M respectively. The overall better performance of the Ni-CaAl catalyst over that of the Ni-Al was attributed to the added CaO reducing the acidity of the Al2O3 support, which provided a superior resistance to persistent coke formation. Unlike Rh-Al, the R-M and RC-M exhibited low steam conversions to H2 and CH4, evidencing little activity in water gas shift and methanation. However, the monolith catalysts showed no significant loss of activity, unlike Ni-Al. Both catalytic PPB (small reactor volumes) and monolith structures (ease of flow, strength, and stability) offer different advantages, thus Rh and Ni catalysts with new supports and structures combining these advantages for their suitability to the scale of local biomass resources could help the future sustainable use of biomasses and their bio-oils as storage friendly and energy dense sources of green hydrogen. Full article
(This article belongs to the Special Issue Catalytic Reforming for Syngas and H2 Productions)
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17 pages, 3390 KiB  
Article
The Effect of ZrO2 as Different Components of Ni-Based Catalysts for CO2 Reforming of Methane and Combined Steam and CO2 Reforming of Methane on Catalytic Performance with Coke Formation
by Wassachol Sumarasingha, Somsak Supasitmongkol and Monrudee Phongaksorn
Catalysts 2021, 11(8), 984; https://doi.org/10.3390/catal11080984 - 17 Aug 2021
Cited by 11 | Viewed by 2494
Abstract
The role of ZrO2 as different components in Ni-based catalysts for CO2 reforming of methane (CRM) has been investigated. The 10 wt.% Ni supported catalysts were prepared with ZrO2 as a support using a co-impregnation method. As a promoter (1 [...] Read more.
The role of ZrO2 as different components in Ni-based catalysts for CO2 reforming of methane (CRM) has been investigated. The 10 wt.% Ni supported catalysts were prepared with ZrO2 as a support using a co-impregnation method. As a promoter (1 wt.% ZrO2) and a coactive component (10 wt.% ZrO2), the catalysts with ZrO2 were synthesized using a co-impregnation method. To evaluate the effect of the interaction, the Ni catalyst with ZrO2 as a coactive component was prepared by a sequential impregnation method. The results revealed that the activity, the selectivity, and the anti-coking ability of the catalyst depend upon the ZrO2 content, the Ni-ZrO2 interaction, basicity, and oxygen mobility of each catalyst resulting in different Ni dispersion and oxygen transfer pathway from ZrO2 to Ni. According to the characterization and catalytic activation results, the Ni catalyst with low ZrO2 content (as a promoter) presented highest selectivity toward CO owning to the high number of weak and moderate basic sites that enhance the CO2 activation-dissociation. The lowest activity (CH4 conversion ≈ 40% and CO2 conversion ≈ 39%) with the relatively high quantity of total coke formation (the weight loss of the spent catalyst in TGA curve ≈ 22%) of the Ni catalyst with ZrO2 as a support is ascribed to the lowest Ni dispersion due to the poor Ni-ZrO2 interaction and less oxygen transfer from ZrO2 to the deposited carbon on the Ni surface. The effect of a poor Ni-ZrO2 interaction on the catalytic activity was deducted by decreasing ZrO2 content to 10 wt.% (as a coactive component) and 1 wt.% (as a promoter). Although Ni catalysts with 1 wt.% and 10 wt.% ZrO2 provided similar oxygen mobility, the lack of oxygen transfer to coke during CRM process on the Ni surface was still indicated by the growth of carbon filament when the catalyst was prepared by co-impregnation method. When the catalyst was prepared by a sequential impregnation, the intimate interaction of Ni and ZrO2 for oxygen transfer was successfully developed through a ZrO2-Al2O3 composite. The interaction in this catalyst enhanced the catalytic activity (CH4 conversion ≈ 54% and CO2 conversion ≈ 50%) and the oxygen transport for carbon oxidation (the weight loss of the spent catalyst in TGA curve ≈ 7%) for CRM process. The Ni supported catalysts with ZrO2 as a promoter prepared by co-impregnation and with ZrO2 as a coactive component prepared by a sequential impregnation were tested in combined steam and CO2 reforming of methane (CSCRM). The results revealed that the ZrO2 promoter provided a greater carbon resistance (coke = 1.213 mmol·g−1) with the subtraction of CH4 and CO2 activities (CH4 conversion ≈ 28% and CO2 conversion ≈ %) due to the loss of active sites to the H2O activation-dissociation. Thus, the H2O activation-dissociation was promoted more efficiently on the basic sites than on the vacancy sites in CSCRM. Full article
(This article belongs to the Special Issue Catalytic Reforming for Syngas and H2 Productions)
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14 pages, 3969 KiB  
Article
Experimental Study on Sulfur Deactivation and Regeneration of Ni-Based Catalyst in Dry Reforming of Biogas
by Rei-Yu Chein, Yen-Chung Chen and Wei-Hsin Chen
Catalysts 2021, 11(7), 777; https://doi.org/10.3390/catal11070777 - 26 Jun 2021
Cited by 10 | Viewed by 2310
Abstract
The dry reforming of methane (DRM) using biogas and a Ni-based catalyst for syngas production was studied experimentally in this study under the presence of H2S. Using the nonpoisoned DRM performance as a comparison basis, it was found that the catalyst [...] Read more.
The dry reforming of methane (DRM) using biogas and a Ni-based catalyst for syngas production was studied experimentally in this study under the presence of H2S. Using the nonpoisoned DRM performance as a comparison basis, it was found that the catalyst deactivation by the sulfur chemisorption onto the catalyst surface depends on both reaction temperature and time. With low reaction temperatures, a complete sulfur coverage was resulted and could not be regenerated. With higher reaction temperatures, the H2S coverage decreased, and the poisoned catalysts could be regenerated. The experimental results also indicated that a catalyst deactivation could not be avoided by using the bi-reforming of methane by adding O2 or H2O simultaneously in the reactant due to the stronger chemisorption capability of sulfur. The catalyst could only be regenerated after it was poisoned. The experimental results indicated that the high-temperature oxidation process was the most effective process for regenerating the poisoned catalyst. Full article
(This article belongs to the Special Issue Catalytic Reforming for Syngas and H2 Productions)
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14 pages, 8422 KiB  
Article
The Effect of Hydrogen Production Rate of the via Different Preparation of Co-Based Catalyst with Sodium Borohydride
by Jyun-Lin Lai, Win-Jet Luo, Yean-Der Kuan and Pai-Jun Zhang
Catalysts 2021, 11(5), 528; https://doi.org/10.3390/catal11050528 - 21 Apr 2021
Cited by 5 | Viewed by 2379
Abstract
This study processed the water vapor entrained in the NaBH4 hydrogen production reaction inside the primary hydrogen production tank through the secondary hydrogen production tank, in order to increase total hydrogen production. γ-Al2O3 was used as the carrier for [...] Read more.
This study processed the water vapor entrained in the NaBH4 hydrogen production reaction inside the primary hydrogen production tank through the secondary hydrogen production tank, in order to increase total hydrogen production. γ-Al2O3 was used as the carrier for the hydrolytic hydrogen production reaction in the primary hydrogen production tank. The reaction was chelated with metal catalyst Co2+ at different concentrations to produce the catalyst. Next, the adopted catalyst concentration and different catalyst bed temperatures were tested. The secondary hydrogen production tank was tested using NaBH4 powder and multiple NaBH4+ Co2+ mixed powders at different ratios. The powder was refined by ball milling with different steel ball ratios to enlarge the contact area between the water vapor and powder. The ball milling results from carriers at different concentrations, different catalyst bed temperatures, NaBH4+ Co2+ mixed powders in different ratios and different steel ball ratios were discussed as the hydrogen production rate and hydrogen production in relation to the hydrolytic hydrogen production reaction. The experimental results show that the hydrolytic hydrogen production reaction is good when 45 wt% Co2+/γ-Al2O3 catalyst is placed in the primary hydrogen production tank at a catalyst bed temperature of 55 °C. When the NaBH4+ Co2+ mixed powder in a ratio of 7:3 and steel balls in a ratio of 1:4 were placed in the secondary hydrogen production tank for 2 h of ball milling, the hydrogen production increased favorably. The hydrogen storage can be increased effectively without wasting the water vapor entrained in the hydrolytic hydrogen production reaction, and the water vapor effect on back-end storage can be reduced. Full article
(This article belongs to the Special Issue Catalytic Reforming for Syngas and H2 Productions)
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15 pages, 6346 KiB  
Article
Biogas Reforming over Al-Co Catalyst Prepared by Solution Combustion Synthesis Method
by Manapkhan Zhumabek, Galina Xanthopoulou, Svetlana A. Tungatarova, Tolkyn S. Baizhumanova, George Vekinis and Dmitry Yu. Murzin
Catalysts 2021, 11(2), 274; https://doi.org/10.3390/catal11020274 - 18 Feb 2021
Cited by 7 | Viewed by 2332
Abstract
The results of carbon dioxide reforming of CH4 (model biogas) on catalysts prepared by solution combustion synthesis (SCS) and impregnation of moisture capacity methods are presented. Investigation of the activity of catalysts synthesized from initial mixtures of Co(NO3)2-Al(NO [...] Read more.
The results of carbon dioxide reforming of CH4 (model biogas) on catalysts prepared by solution combustion synthesis (SCS) and impregnation of moisture capacity methods are presented. Investigation of the activity of catalysts synthesized from initial mixtures of Co(NO3)2-Al(NO3)3-urea of different compositions was carried out for the production of synthesis-gas, and SCS and traditional incipient wetness impregnation catalyst preparation methods were compared. The methane conversion reached 100%, and the conversion of CO2 increased to 86.2%, while the yield of H2 and CO was 99.2% and 85.4%, respectively, at 900 °C. It was found that CoAl2O4 spinel formation was due to substitution of Al3+ with Co2+ cations. Consequently, CoAl2O4 lattice parameters increased, since the ionic radius of Al3+ (0.51 Å) less than Cο2+ (0.72 Å). Advantages of SCS catalysts in comparison with catalysts prepared by the traditional incipient wetness impregnation method in dry reforming of methane were shown. The aim of this work is to develop a new catalyst for the conversion of model biogas into synthesis gas, which will contribute to the organization of a new environmentally friendly, energy-saving production in the future. Full article
(This article belongs to the Special Issue Catalytic Reforming for Syngas and H2 Productions)
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Review

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28 pages, 5828 KiB  
Review
Catalytic Upgrading of Clean Biogas to Synthesis Gas
by Nicola Schiaroli, Martina Battisti, Patricia Benito, Giuseppe Fornasari, Amalio Giovanni Di Gisi, Carlo Lucarelli and Angelo Vaccari
Catalysts 2022, 12(2), 109; https://doi.org/10.3390/catal12020109 - 18 Jan 2022
Cited by 6 | Viewed by 3574
Abstract
Clean biogas, produced by anaerobic digestion of biomasses or organic wastes, is one of the most promising substitutes for natural gas. After its purification, it can be valorized through different reforming processes that convert CH4 and CO2 into synthesis gas (a [...] Read more.
Clean biogas, produced by anaerobic digestion of biomasses or organic wastes, is one of the most promising substitutes for natural gas. After its purification, it can be valorized through different reforming processes that convert CH4 and CO2 into synthesis gas (a mixture of CO and H2). However, these processes have many issues related to the harsh conditions of reaction used, the high carbon formation rate and the remarkable endothermicity of the reforming reactions. In this context, the use of the appropriate catalyst is of paramount importance to avoid deactivation, to deal with heat issues and mild reaction conditions and to attain an exploitable syngas composition. The development of a catalyst with high activity and stability can be achieved using different active phases, catalytic supports, promoters, preparation methods and catalyst configurations. In this paper, a review of the recent findings in biogas reforming is presented. The different elements that compose the catalytic system are systematically reviewed with particular attention on the new findings that allow to obtain catalysts with high activity, stability, and resistance towards carbon formation. Full article
(This article belongs to the Special Issue Catalytic Reforming for Syngas and H2 Productions)
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