Catalytic halogenation of methane: a dream reaction with practical scope?

Paunović, Vladimir; Pérez‐Ramírez, Javier

doi:10.1039/c9cy00625g

Cited by 30 publications

(52 citation statements)

References 46 publications

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“…It was also shown that at a lower CH 4 /Cl 2 ratio, the zeolite NaHY is less selective for methyl chloride than at a higher ratio [43]. This observation is in agreement with [40], where a CH 4 /Cl 2 ratio of 2.43 was used and zeolites were not very selective for methyl chloride. Higher selectivity was achieved at lower conversions of methane.…”

Section: Non-oxidative Catalytic Halogenationsupporting

confidence: 74%

“…The methane molecule can react with the Cl + ion or with the transitional state from Brønsted acid site to Al − OCl + Si species. This mechanism is in contrast with the one proposed by a more recent study [40] where the radical mechanism was also assumed for zeolite catalysts. It was also shown that at a lower CH 4 /Cl 2 ratio, the zeolite NaHY is less selective for methyl chloride than at a higher ratio [43].…”

Section: Non-oxidative Catalytic Halogenationcontrasting

confidence: 71%

“…Gorin et al [39] studied methane chlorination kinetics in reactions between methane and molten salt consisting of KCl-CuCl-CuCl 2 in 1948. This area of research is still active today [40,41]. The highest selectivity achieved for CH 3 Br was 99% and 20% conversion of methane over 20% SbOF 3 /Al 2 O 3 at 200 • C, at GHSV (gas hour space velocity) of 100 mL/(g h) and CH 4 /Br 2 ratio of 5.…”

Section: Non-oxidative Catalytic Halogenationmentioning

confidence: 99%

“…Acidic zeolites with low SiO 2 /Al 2 O 3 could be appropriate catalysts for selective methane bromination. Recently, a broad range of zeolite and zeolite-supported catalysts was screened for bromination and chlorination of methane [40]. It was found that zeolite catalysts are more active in the case of chlorination than in the case of bromination.…”

Section: Non-oxidative Catalytic Halogenationmentioning

confidence: 99%

“…This is mainly observed in the chlorination reaction, while in the case of bromination the production of Br radicals has a limited effect on the reaction. In the case of methane chlorination, there is also an additional effect of shape selectivity of zeolite pores, where the sum of kinetic diameters of methane and chlorine radicals is approximately the same as the pore size in some zeolites (e.g., HZSM-5 and beta) [40]. These observations therefore suggest a totally different mechanism of activation on zeolites compared to previously mentioned catalysts, i.e., SbOF 3 /Al 2 O 3 and SZr(25)SBA-15, although strong Brønsted acid sites are present in the zeolites with a low SiO 2 /Al 2 O 3 ratio.…”

Section: Non-oxidative Catalytic Halogenationmentioning

confidence: 99%

See 4 more Smart Citations

A Review of Methane Activation Reactions by Halogenation: Catalysis, Mechanism, Kinetics, Modeling, and Reactors

et al. 2020

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Methane is the central component of natural gas, which is globally one of the most abundant feedstocks. Due to its strong C–H bond, methane activation is difficult, and its conversion into value-added chemicals and fuels has therefore been the pot of gold in the industry and academia for many years. Industrially, halogenation of methane is one of the most promising methane conversion routes, which is why this paper presents a comprehensive review of the literature on methane activation by halogenation. Homogeneous gas phase reactions and their pertinent reaction mechanisms and kinetics are presented as well as microkinetic models for methane reaction with chlorine, bromine, and iodine. The catalysts for non-oxidative and oxidative catalytic halogenation were reviewed for their activity and selectivity as well as their catalytic action. The highly reactive products of methane halogenation reactions are often converted to other chemicals in the same process, and these multi-step processes were reviewed in a separate section. Recent advances in the available computational power have made the use of the ab initio calculations (such as density functional theory) routine, allowing for in silico calculations of energy profiles, which include all stable intermediates and the transition states linking them. The available literature on this subject is presented. Lastly, green processes and the production of fuels as well as some unconventional methods for methane activation using ultrasound, plasma, superacids, and light are also reviewed.

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Section: Non-oxidative Catalytic Halogenationsupporting

confidence: 74%

Section: Non-oxidative Catalytic Halogenationcontrasting

confidence: 71%

Section: Non-oxidative Catalytic Halogenationmentioning

confidence: 99%

Section: Non-oxidative Catalytic Halogenationmentioning

confidence: 99%

Section: Non-oxidative Catalytic Halogenationmentioning

confidence: 99%

See 3 more Smart Citations

A Review of Methane Activation Reactions by Halogenation: Catalysis, Mechanism, Kinetics, Modeling, and Reactors

et al. 2020

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Mechanochemical Radical Transformations in Organic Synthesis

Sheikhaleslami,

Sperry

2024

Chemistry A European J

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Electrocatalytic dehalogenation in the applications of organic synthesis and environmental degradation

Zhao,

Yao,

Zhang

et al. 2024

EcoEnergy

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Electrocatalytic dehalogenation technology is a promising approach for the synthesis of chemicals (such as pesticides and pharmaceutical intermediates) and the disposal of halogenated organic pollutants. Compared with the traditional chemical reduction technology, the electrocatalytic reduction dehalogenation method has the advantages of high efficiency, controllable operation, and reduced secondary pollution. This review systematically consolidates the recent advances in the electrocatalytic dehalogenation in the application of organic synthesis and environmental degradation, focusing on the involved mechanisms, and influences factors (e.g., electrocatalysts, solution environment, and reaction conditions) on the performance of electrocatalytic dehalogenation. Furthermore, the latest characterization and analytical methods and the industrial application of electrocatalytic dehalogenation technology are summarized. Lastly, the existing challenges and perspectives are proposed for efficient electrocatalytic dehalogenation.

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Catalytic halogenation of methane: a dream reaction with practical scope?

Abstract: Methane halogenation over solid materials is dominated by radical intermediates, the stabilization of which through confinement effects enhances the activity.

Cited by 30 publications

References 46 publications

A Review of Methane Activation Reactions by Halogenation: Catalysis, Mechanism, Kinetics, Modeling, and Reactors

A Review of Methane Activation Reactions by Halogenation: Catalysis, Mechanism, Kinetics, Modeling, and Reactors

Mechanochemical Radical Transformations in Organic Synthesis

Electrocatalytic dehalogenation in the applications of organic synthesis and environmental degradation

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