Dry reforming of methane using various catalysts in the process: review

Singh, Rattanvir; Dhir, Amit; Mohapatra, S.K.; Mahla, Sunil Kumar

doi:10.1007/s13399-019-00417-1

Cited by 73 publications

(34 citation statements)

References 133 publications

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“…The activity of catalysts for dry reforming depends on a range of factors as the active metal (species, reducibility, particle size), the support (kind of support, surface area, acidity, basicity, oxygen storage capacity) and interaction of both . Several reviews summarized the developments in the field of catalyst materials for dry reforming of methane and focused on the properties and catalytic behavior of different catalyst systems. While different active metals have been considered, most of the discussed systems can be either assigned to noble metals (Rh, Ru, Pt, Ir, and Pd) or base metals (Ni, Co).…”

Section: Introductionsupporting

confidence: 87%

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Catalytic Dry Reforming of Methane: Insights from Model Systems

Wittich¹,

et al. 2020

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Catalytic dry reforming under industrially relevant conditions of high pressures and high temperatures poses severe challenges towards catalyst materials and process engineering. The demanding conditions under which the reaction is performed lead to a coupling of reactions occurring in the gas phase and reactions which are catalyzed by the material employed as catalyst. A profound analysis of the mechanisms occurring in gas phase and resulting products from gas phase reactions is key to understanding part of the challenges that any catalyst material, irrespective of its nature, will have to cope with. The deposition of coke on an active catalyst is as well one of the most limiting factors for catalyst lifetime and catalyst activity in dry reforming. Therefore, an understanding of the thermodynamics behind coke formation and an intricate description of the mechanisms driving the evolution of coke is a vital piece of the picture. Acid-base properties of the catalyst material and the role and nature of the active metal do also need to be considered. A large part of the review deals with mechanisms which are relevant for coke gasification and insights into materials properties, which are relevant to allow for reaction pathways along these lines. The review article focusses on research results which have been achieved using model systems -typically the analysis of model systems is a more rewarding exercise compared to fully formulated industrial catalyst systems, as here more elucidating structure-property relationships can be drawn. Additionally the article discusses dry methane reforming in the context of alternative syngas generation technologies and attempts to create an application perspective for the reader in the context of a sustainable approach towards carbon capture and storage.

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Section: Introductionsupporting

confidence: 87%

“…This phenomenon has already been observed in 1928 by Fischer and Tropsch over Ni and Co catalysts . Numerous reviews on DRM have been written in recent years which mainly deal with different types of catalysts that are said to be less affected by coke formation …”

Section: Introductionmentioning

confidence: 99%

Catalytic Dry Reforming of Methane: Insights from Model Systems

Wittich¹,

et al. 2020

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“…It can be used directly as fuel or converted to other hydrocarbons to produce valuable ultra-clean fuels and products such as methanol, diesel, gasoline, kerosene and naphtha via Fischer-Tropsch synthesis, and other reactions [3,4]. In addition to syngas, there are ongoing efforts to make the process more economical by producing valuable byproducts such as solid carbon as added value [5,6]. Despite its numerous advantages, DRM is a highly endothermic process (Equation (1)) that requires high temperatures of around 700 • C to achieve equilibrium conversions of CH 4 and CO 2 [7].…”

Section: Introductionmentioning

confidence: 99%

Mechanistic Insights for Dry Reforming of Methane on Cu/Ni Bimetallic Catalysts: DFT-Assisted Microkinetic Analysis for Coke Resistance

et al. 2020

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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.

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“…Due to the high thermodynamic stability of CO 2 and chemical inertness of CH bonds in lower alkanes, this reaction normally requires high temperatures (>600 °C). [40,41] To develop more sustainable catalysts, lowering the reaction temperature is essential but remains challenging. [42] At a desirable low temperature for this reaction (400 °C), [42] conventionally prepared catalysts (Ni convent , ≈5/95 at% Ni/Si, ≈21 nm Ni crystals) shows no detectable activity, which can be attributed to their lower metal loading.…”

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confidence: 99%

Shape‐Preserving Chemical Conversion of Architected Nanocomposites

et al. 2020

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microscopic 3D shapes has remained challenging. Synthesis inherently entangles shape and composition; hence, current assembly routes offer control over either 3D shape or composition, but not both. In principle, chemically converting existing 3D shapes to a specified composition allows control over both the chemical composition and 3D geometry. The viability of this strategy is indicated by naturally occurring geochemical fossilization processes, [1] and laboratory demonstrations of shape-preserving ion-exchange and oxidation/reduction reactions on individual and ensembles of nanocrystals, as well as biominerals. [5,23-28] Nevertheless, conversion of arbitrary microscopic architectures is still challenging as conversion is diffusion-limited and slow, and significant changes in the atomistic unit cells could yield uncontrollable dissolution/ recrystallization, large deformations, and even fracture failure. We recognize that successful conversion reactions require a paradoxical combination of reactivity and stability to enable: i) diffusion of reactants and products in the solid phase, ii) crystal lattice rearrangements and unit-cell volume changes, while iii) preserving the overall 3D shape. We thus hypothesize that nanocomposites consisting of nanocrystals in an amorphous matrix have excellent characteristics to overcome these issues. Traditionally, nanocomposites have mainly been studied for their excellent mechanical properties. [1,2,5,6,13,14] Importantly, coprecipitation of carbonate salts Forging customizable compounds into arbitrary shapes and structures has the potential to revolutionize functional materials, where independent control over shape and composition is essential. Current self-assembly strategies allow impressive levels of control over either shape or composition, but not both, as self-assembly inherently entangles shape and composition. Herein, independent control over shape and composition is achieved by chemical conversion reactions on nanocrystals, which are first self-assembled in nanocomposites with programmable microscopic shapes. The multiscale character of nanocomposites is crucial: nanocrystals (5-50 nm) offer enhanced chemical reactivity, while the composite layout accommodates volume changes of the nanocrystals (≈25%), which together leads to complete chemical conversion with full shape preservation. These reactions are surprisingly materials agnostic, allowing a large diversity of chemical pathways, and development of conversion pathways yielding a wide selection of shape-controlled transition metal chalcogenides (cadmium, manganese, iron, and nickel oxides and sulfides). Finally, the versatility and application potential of this strategy is demonstrated by assembling: 1) a scalable and highly reactive nickel catalyst for the dry reforming of butane, 2) an agile magnetic-controlled particle, and 3) an electron-beam-controlled reversible microactuator with sub-micrometer precision. Previously unimaginable customization of shape and composition is now achievable for assembling advance...

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Dry reforming of methane using various catalysts in the process: review

Cited by 73 publications

References 133 publications

Catalytic Dry Reforming of Methane: Insights from Model Systems

Catalytic Dry Reforming of Methane: Insights from Model Systems

Mechanistic Insights for Dry Reforming of Methane on Cu/Ni Bimetallic Catalysts: DFT-Assisted Microkinetic Analysis for Coke Resistance

Shape‐Preserving Chemical Conversion of Architected Nanocomposites

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