Mechanism of the Methylchlorosilane Reaction:  Improved Lab Reactor Design and Kinetic Data

Bablin, John M.; Lewis, Lionel S.; Bui, Pierre; Gardner, Martha

doi:10.1021/ie0203330

Cited by 24 publications

(34 citation statements)

References 14 publications

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“…The reaction rate highly increases with the reaction temperature, especially after it exceeds 300°C. The change trend is similar to that proposed by Bablin et al 7 , not to that by Ward et al 1 , who thought that the temperature had no effect on product distribution. According to the Arrhenius equation, as the activation energy of Eq.…”

Section: Resultssupporting

confidence: 89%

“…Numerous reports have appeared on the kinetics of the reaction 3 4 . The influence of the contents of the catalysts 5 and promoters such as zinc 6 , tin 1 7 , phosphorus, stannum 5 and aluminum 2 , the structure of the catalysts 8 on the reaction kinetics have been experimentally investigated in a flow reactor, a fixed bed reactor or a fluidized bed reactor. De Cooker et al 9 10 has studied the effect of the addition of hydrogen and oxygen on the product composition and an overall selectivity of the reaction.…”

mentioning

confidence: 99%

“…With good transport character, it is usually thought that the reaction activity and M2 selectivity in the fluidized bed reactor (FBR) can be higher than that in the fixed-bed reactor (FXBR). But relevant more studies were only carried out under certain operating parameters 7 13 14 15 . The characters which influence the transport process, such as the particle size, superficial gas velocity and bed height, were less discussed.…”

mentioning

confidence: 99%

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Effect of Bed Characters on the Direct Synthesis of Dimethyldichlorosilane in Fluidized Bed Reactor

Zhang

Duan

Chen

et al. 2015

Sci Rep

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This paper presents the numerical investigation of the effects of the general bed characteristics such as superficial gas velocities, bed temperature, bed heights and particle size, on the direct synthesis in a 3D fluidized bed reactor. A 3D model for the gas flow, heat transfer, and mass transfer was coupled to the direct synthesis reaction mechanism verified in the literature. The model was verified by comparing the simulated reaction rate and dimethyldichlorosilane (M2) selectivity with the experimental data in the open literature and real production data. Computed results indicate that superficial gas velocities, bed temperature, bed heights, and particle size have vital effect on the reaction rates and/or M2 selectivity.

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Section: Resultssupporting

confidence: 89%

mentioning

confidence: 99%

mentioning

confidence: 99%

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Effect of Bed Characters on the Direct Synthesis of Dimethyldichlorosilane in Fluidized Bed Reactor

Zhang

Duan

Chen

et al. 2015

Sci Rep

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“…1). Methyl chloride is an important reactant in a number of chemical processes, such as in the production of silicon [3] or methanol [4]. Potentially, methyl chloride could also be used as the basis of the synthesis of higher hydrocarbons, whereby the HCl set free in the process can be reused for the oxidative chlorination [4][5][6].…”

Section: Introductionmentioning

confidence: 99%

Modified Lanthanum Catalysts for Oxidative Chlorination of Methane

et al. 2009

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Mixtures of LaOCl and LaCl 3 are promising catalysts for oxidative chlorination of methane to methyl chloride. The influence of metal dopants such as Co, Ni and Ce, which form stable chlorides under anticipated reaction conditions, on physicochemical and catalytic properties was explored. The presence of markedly redox-active dopants such as cobalt and cerium lead to a higher rate of methane conversion. However, the formed methyl chloride is strongly adsorbed and directly oxidized to CO leading to low methyl chloride selectivity. Doping with nickel weakens, in contrast, the interaction with methyl chloride leading to high methyl chloride selectivity.

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“…1,2 In this reaction, gaseous methyl chloride (MeCl) reacts with silicon (Si) in the presence of Cu-based catalysts as following: [3][4][5] Among these products, dimethyldichlorosilane ((CH 3 ) 2 SiCl 2 , M2) is the most important monomer for the production of organosilane products in industry. 1,2 In this reaction, gaseous methyl chloride (MeCl) reacts with silicon (Si) in the presence of Cu-based catalysts as following: [3][4][5] Among these products, dimethyldichlorosilane ((CH 3 ) 2 SiCl 2 , M2) is the most important monomer for the production of organosilane products in industry.…”

Section: Introductionmentioning

confidence: 99%

Heterojunctions generated in SnO₂–CuO nanocatalysts for improved catalytic property in the Rochow reaction

Shanying

Wang

et al. 2015

RSC Adv.

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We report the improved catalytic performance of SnO 2 -CuO hybrid nanocatalysts synthesized by rationally designing and controlling the local heterojunctions structure. The SnO 2 nanoparticles (NPs) decorated CuO nanorods (NRs) (SnO 2 -CuO) with a mace-like structure and with various CuO : SnO 2 ratios were prepared via depositing pre-synthesized SnO 2 NPs on CuO NRs in the presence of polyvinylpyrrolidone molecules. The CuO NRs were obtained by a facile hydrothermal reaction using Cu(NO 3 ) 2 •3H 2 O as the precursor. The samples were characterized by X-ray diffraction, transmission electron microscopy, scanning electron microscopy, X-ray photoelectron spectroscopy, and temperature-programmed reduction analyses. The results indicated that in the SnO 2 -CuO hybrid nanostructures, the heterojunctions were well generated as the SnO 2 NPs were well dispersed on the CuO NRs. Their catalytic performances were then explored via the Rochow reaction, in which solid silicon (Si) reacts with gaseous methyl chloride (MeCl) to produce dimethyldichlorosilane (M2). Compared to discrete CuO and SnO 2 as well as their physical mixture, the SnO 2 -CuO hybrids exhibit significantly enhanced M2 selectivity and Si conversion because of the enhanced synergistic interaction between SnO 2 and CuO due to the generated heterojunctions.This work demonstrates that the performance of heterogeneous catalysts can be improved by carefully designing and controlling its structures even maintaining the composition unchanged.CuO microspheres 17 have been prepared in our group as model catalysts for the Rochow reaction, and found that their catalytic performance mainly depends on the chemical composition, 18 particles size, 19 and surface structure. 16 However, the above catalysts still suffer from low M2 selectivity and/or Si conversion, which seriously hinder their further application. Therefore, more efficient Cu-based catalysts should be developed.Recently, CuO-based hetero-structured hybrid materials have caused strong attention owing to their distinct properties and high diversity in structure and composition. For instance, Avgouropoulos et al. prepared a series of CuO-CeO 2 catalysts which exhibited much better catalytic performance for the selective oxidation of CO than CuO alone. 20 Li et al. observed that the CuO-ZnO-ZrO 2 catalysts synthesized by a surfactant-assisted coprecipitation method showed higher catalytic activity than that of sole CuO as a result of more intimate contact at the interface between Cu species and ZnO and/or ZrO 2 . 21 More recently, we have grown flower-like ZnO on urchin-like CuO microspheres using a simple solvothermal method, and the hierarchical structure displayed better catalytic properties in M2 synthesis in comparison with the single CuO phase, probably because of the enhanced synergistic effect between ZnO and CuO. 22 However, the composite particles were still in the micrometer scale with limited particle contact and weak synergistic effect.On the other hand, to date there are few reports on preparing Cu...

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Mechanism of the Methylchlorosilane Reaction: Improved Lab Reactor Design and Kinetic Data

Cited by 24 publications

References 14 publications

Effect of Bed Characters on the Direct Synthesis of Dimethyldichlorosilane in Fluidized Bed Reactor

Effect of Bed Characters on the Direct Synthesis of Dimethyldichlorosilane in Fluidized Bed Reactor

Modified Lanthanum Catalysts for Oxidative Chlorination of Methane

Heterojunctions generated in SnO₂–CuO nanocatalysts for improved catalytic property in the Rochow reaction

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Mechanism of the Methylchlorosilane Reaction: Improved Lab Reactor Design and Kinetic Data

Cited by 24 publications

References 14 publications

Effect of Bed Characters on the Direct Synthesis of Dimethyldichlorosilane in Fluidized Bed Reactor

Effect of Bed Characters on the Direct Synthesis of Dimethyldichlorosilane in Fluidized Bed Reactor

Modified Lanthanum Catalysts for Oxidative Chlorination of Methane

Heterojunctions generated in SnO2–CuO nanocatalysts for improved catalytic property in the Rochow reaction

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Product

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Heterojunctions generated in SnO₂–CuO nanocatalysts for improved catalytic property in the Rochow reaction