scholarly journals Elucidating the Role and Interplay of Nickel and Molybdenum Carbide Particles Supported on Zeolite Y in Methane-Steam Reforming

2021 ◽  
Author(s):  
Xianghui Zhang ◽  
Su Ha ◽  
Di Wu
Keyword(s):  
High Activity ◽  
Steam Reforming ◽  
Large Scale ◽  
Molybdenum Carbide ◽  
Ostwald Ripening ◽  
Zeolite Y ◽  
Metallic Nickel ◽  
Transition Metal Carbide ◽  
Methane Steam Reforming ◽  
Methane Steam

Methane steam reforming (MSR) reaction is a mature industrial process that has been applied for large-scale hydrogen production. Here, we report the synthesis and characterization, reaction kinetics, and deactivation mechanism of a series of catalysts with metallic nickel (Ni) clusters and molybdenum carbide (Mo2C) particles supported on zeolite Y (Ni-Mo2C/FAU) in MSR reaction at 850 oC. Despite low Ni loading less than 2.4 wt%, MSR on Ni-Mo2C/FAU exhibits high activity and stability, yet deactivation of Ni-FAU (the sample without Mo2C) is significant. Further investigations elucidate that the catalyst deactivation is caused by Ni particle sintering via Ostwald ripening instead of coking, and steam induces hydroxylated Ni surface that accelerates sintering. Moreover, encapsulated Mo2C boosts the activity and stability of Ni on zeolite Y by enhancing CH4 activation rather than activating H2O. The interplays among Mo2C and Ni particles dynamically balance the carbon formation and consumption rates, and inhibit Ni sintering. This study enables insights into an alternative design principle of transition metal carbide – Ni catalysts with high activity and stability for effective MSR by tuning the compositional, structural, and interfacial factors.

scholarly journals A Short Review on Ni Based Catalysts and Related Engineering Issues for Methane Steam Reforming

Catalysts ◽  
2020 ◽  
Vol 10 (3) ◽  
pp. 352 ◽  
Author(s):  
Eugenio Meloni ◽  
Marco Martino ◽  
Vincenzo Palma
Keyword(s):  
Steam Reforming ◽  
Large Scale ◽  
Short Review ◽  
Raw Material ◽  
Methane Steam Reforming ◽  
Thermal Exchange ◽  
Structured Catalysts ◽  
Methane Steam ◽  
Load Fluctuation ◽  
Hydrogen Station

Hydrogen is an important raw material in chemical industries, and the steam reforming of light hydrocarbons (such as methane) is the most used process for its production. In this process, the use of a catalyst is mandatory and, if compared to precious metal-based catalysts, Ni-based catalysts assure an acceptable high activity and a lower cost. The aim of a distributed hydrogen production, for example, through an on-site type hydrogen station, is only reachable if a novel reforming system is developed, with some unique properties that are not present in the large-scale reforming system. These properties include, among the others, (i) daily startup and shutdown (DSS) operation ability, (ii) rapid response to load fluctuation, (iii) compactness of device, and (iv) excellent thermal exchange. In this sense, the catalyst has an important role. There is vast amount of information in the literature regarding the performance of catalysts in methane steam reforming. In this short review, an overview on the most recent advances in Ni based catalysts for methane steam reforming is given, also regarding the use of innovative structured catalysts.

Modulating oxidation state of Ni/CeO2 catalyst for steam methane reforming: a theoretical prediction with experimental verification

2021 ◽  
Author(s):  
Chan Wu ◽  
Zhourong Xiao ◽  
Li Wang ◽  
Guozhu Li ◽  
Xiangwen Zhang ◽  
...  
Keyword(s):  
Theoretical Prediction ◽  
High Activity ◽  
Steam Reforming ◽  
Experimental Verification ◽  
Rational Design ◽  
Methane Steam Reforming ◽  
Methane Reforming ◽  
Steam Methane Reforming ◽  
Steam Methane ◽  
Methane Steam

Rational design of partially oxidized Ni/CeO2 with both high activity and good stability by DFT for efficient methane steam reforming.

scholarly journals Reaction Pathway for Coke-Free Methane Steam Reforming on a Ni/CeO2 Catalyst: Active Sites and Role of Metal-Support Interactions

2021 ◽  
Author(s):  
Agustin Salcedo ◽  
Pablo Lustemberg ◽  
Ning Rui ◽  
Robert M. Palomino ◽  
Zongyuan Liu ◽  
...  
Keyword(s):  
High Activity ◽  
Steam Reforming ◽  
Active Sites ◽  
Density Functional ◽  
Ambient Pressure ◽  
Carbon Accumulation ◽  
Methane Steam Reforming ◽  
Severe Problem ◽  
Methane Steam ◽  
Water Activation

<p>Methane steam reforming (MSR) plays a key role in the production of syngas and hydrogen from natural gas. The increasing interest in the use of hydrogen for fuel cell applications demands the development of catalysts with high activity at reduced operating temperatures. Ni-based catalysts are promising systems because of their high activity and low cost, but coke formation generally poses a severe problem. Studies of ambient-pressure X-ray photoelectron spectroscopy (AP-XPS) indicate that CH<sub>4</sub>/H<sub>2</sub>O gas mixtures react with Ni/CeO<sub>2</sub>(111) surfaces to form OH, CH<i><sub>x</sub></i> and CH<i><sub>x</sub></i>O at 300 K. All these species are easy to form and desorb at temperatures below 700 K when the rate of the MSR process accelerates. Density functional theory (DFT) modeling of the reaction over ceria-supported small Ni nanoparticles predicts relatively low activation barriers between 0.3–0.7 eV for the complete dehydrogenation of methane to carbon and the barrierless activation of water at interfacial Ni sites. Hydroxyls resulting from water activation allow CO formation via a COH intermediate with a barrier of about 0.9 eV, which is much lower than that through a pathway involving lattice oxygen from ceria. Neither methane nor water activation are rate-determining steps, and the OH-assisted CO formation through the COH intermediate constitutes a low-barrier pathway that prevents carbon accumulation. The interaction between Ni and the ceria support and the low metal loading are crucial for the reaction to proceed in a coke-free and efficient way. These results could pave the way for further advances in the design of stable and highly active Ni-based catalysts for hydrogen production.</p>

scholarly journals Reaction Pathway for Coke-Free Methane Steam Reforming on a Ni/CeO2 Catalyst: Active Sites and Role of Metal-Support Interactions

2021 ◽  
Author(s):  
Agustin Salcedo ◽  
Pablo Lustemberg ◽  
Ning Rui ◽  
Robert M. Palomino ◽  
Zongyuan Liu ◽  
...  
Keyword(s):  
High Activity ◽  
Steam Reforming ◽  
Active Sites ◽  
Density Functional ◽  
Ambient Pressure ◽  
Carbon Accumulation ◽  
Methane Steam Reforming ◽  
Severe Problem ◽  
Methane Steam ◽  
Water Activation

<p>Methane steam reforming (MSR) plays a key role in the production of syngas and hydrogen from natural gas. The increasing interest in the use of hydrogen for fuel cell applications demands the development of catalysts with high activity at reduced operating temperatures. Ni-based catalysts are promising systems because of their high activity and low cost, but coke formation generally poses a severe problem. Studies of ambient-pressure X-ray photoelectron spectroscopy (AP-XPS) indicate that CH<sub>4</sub>/H<sub>2</sub>O gas mixtures react with Ni/CeO<sub>2</sub>(111) surfaces to form OH, CH<i><sub>x</sub></i> and CH<i><sub>x</sub></i>O at 300 K. All these species are easy to form and desorb at temperatures below 700 K when the rate of the MSR process accelerates. Density functional theory (DFT) modeling of the reaction over ceria-supported small Ni nanoparticles predicts relatively low activation barriers between 0.3–0.7 eV for the complete dehydrogenation of methane to carbon and the barrierless activation of water at interfacial Ni sites. Hydroxyls resulting from water activation allow CO formation via a COH intermediate with a barrier of about 0.9 eV, which is much lower than that through a pathway involving lattice oxygen from ceria. Neither methane nor water activation are rate-determining steps, and the OH-assisted CO formation through the COH intermediate constitutes a low-barrier pathway that prevents carbon accumulation. The interaction between Ni and the ceria support and the low metal loading are crucial for the reaction to proceed in a coke-free and efficient way. These results could pave the way for further advances in the design of stable and highly active Ni-based catalysts for hydrogen production.</p>

Ultra-Low Amounts of Palladium (0.005-0.05 Wt% Pd) Supported on Titania: Remarkable Low-Temperature Activity for NO Reduction with CO and Structure-Function Property Relationships in Methane Oxidation

2020 ◽  
Author(s):  
Konstantin Khivantsev ◽  
Libor Kovarik ◽  
Nicholas R. Jaegers ◽  
János Szanyi ◽  
Yong Wang
Keyword(s):  
Nitric Oxide ◽  
Carbon Monoxide ◽  
Methane Oxidation ◽  
Steam Reforming ◽  
Methane Steam Reforming ◽  
Oxide Reduction ◽  
Water Steam ◽  
Methane Steam ◽  
Anatase Titania ◽  
Nitric Oxide Reduction

<p>Atomically dispersed Pd +2 cations with ultra-dilute loading of palladium (0.005-0.05 wt%) were anchored on anatase titania and characterized with FTIR, microscopy and catalytic tests. CO infrared adsorption produces a sharp, narrow mono-carbonyl Pd(II)-CO band at ~2,130 cm<sup>-1</sup> indicating formation of highly uniform and stable Pd+2 ions on anatase titania. The 0.05 wt% Pd/TiO<sub>2</sub> sample was evaluated for methane combustion under dry and wet (industrially relevant) conditions in the presence and absence of carbon monoxide. Notably, we find the isolated palladium atoms respond dynamically upon oxygen concentration modulation (switching-on and switching off). When oxygen is removed from the wet methane stream, palladium ions are reduced to metallic state by methane and catalyze methane steam reforming instead of complete methane oxidation. Re-admission of oxygen restores Pd<sup>+2</sup> cations and switches off methane steam reforming activity. Moreover, 0.05 wt% Pd/TiO<sub>2</sub> is a competent CO oxidation catalyst in the presence of water steam with 90% CO conversion and TOF ~ 4,000 hr<sup>-1</sup> at 260 ⁰C. </p><p>More importantly, we find that diluting 0.05 wt% Pd/titania sample with titania to ultra-low 0.005 wt% palladium loading produces a remarkably active material for nitric oxide reduction with carbon monoxide under industrially relevant conditions with >90% conversion of nitric oxide at 180 ⁰C (~460 ppm NO and 150 L/g*hr flow rate in the presence of >2% water steam) and TOF ~6,000 hr<sup>-1</sup>. Pd thus outperforms state-of-the-art rhodium containing catalysts with (15-20 times higher rhodium loading; rhodium is ~ 3 times more expensive than palladium). Furthermore, palladium catalysts are more selective towards nitrogen and produce significantly less ammonia relative to the more traditional rhodium catalysts due to lower Pd amount nd lower water-gas-shift activity. Our study is the first example of utilizing ultra-low (0.05 wt% and less) noble metal (Pd) amounts to produce heterogeneous catalysts with extraordinary activity for nitric oxide reduction. This opens up a pathway to study other Pd, Pt and Rh containing materials with ultra-low loadings of expensive noble metals dispersed on titania or titania-coated oxides for industrially relevant nitric oxide abatement.</p>

scholarly journals DFT Benchmark Studies on Representative Species and Poisons of Methane Steam Reforming on Ni(111)

2021 ◽  
Author(s):  
Sai Sharath Yadavalli ◽  
Glenn Jones ◽  
Michail Stamatakis
Keyword(s):  
Steam Reforming ◽  
Graphitic Carbon ◽  
Methane Steam Reforming ◽  
Ni Catalysts ◽  
Methane Steam ◽  
Representative Species ◽  
Industrial Operations ◽  
Major Impediment ◽  
Carbon Based

Ni catalysts used in Methane Steam Reforming (MSR) are highly susceptible to poisoning by carbon-based species, which poses a major impediment to the productivity of industrial operations. These graphitic carbon-like...

scholarly journals Retraction: Computational fluid dynamics modeling of the millisecond methane steam reforming in microchannel reactors for hydrogen production

RSC Advances ◽  
2021 ◽  
Vol 11 (21) ◽  
pp. 12531-12531
Author(s):  
Junjie Chen ◽  
Xuhui Gao ◽  
Longfei Yan ◽  
Deguang Xu
Keyword(s):  
Fluid Dynamics ◽  
Computational Fluid Dynamics ◽  
Hydrogen Production ◽  
Steam Reforming ◽  
Methane Steam Reforming ◽  
Dynamics Modeling ◽  
Computational Fluid Dynamics Modeling ◽  
Microchannel Reactors ◽  
Methane Steam

Retraction of ‘Computational fluid dynamics modeling of the millisecond methane steam reforming in microchannel reactors for hydrogen production’ by Junjie Chen et al., RSC Adv., 2018, 8, 25183–25200, DOI: 10.1039/C8RA04440F.

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