Investigation of reusability and deactivation mechanism of supported platinum catalysts in the practical isomerization of allylic esters

Huang, Qi-An; Murayama, Haruno; Yamamoto, Eiji; Honma, Tetsuo; Tokunaga, Makoto

doi:10.1016/j.cattod.2022.06.007

Cited by 6 publications

(3 citation statements)

References 23 publications

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“…The cesium-based catalysts had stronger selectivity for chloroacetylene, while barium-based catalysts had stronger selectivity for vinyl chloride. The different acidities and alkalinities of catalyst active components led to different product distributions. − …”

Section: Resultsmentioning

confidence: 99%

In Situ Reaction and Mass Spectrometry-Combined Technology for the Catalytic Performance of Cs/Al₂O₃ and Ba/Al₂O₃ in the Dehydrochlorination Reaction of 1,1,2-Trichloroethane

Shen,

Pan,

et al. 2024

Ind. Eng. Chem. Res.

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1,1,2-Trichloroethane (1,1,2-TCE) is a chemical raw material that could be used for cracking to produce 1,2dichloroethylene (1,2-DCE) and 1,1-dichloroethylene (VDC). 1,1-Dichloroethylene had a wide range of industrial applications and was a raw material for various chemical products, such as refrigerant difluorochloroethane, lithium-ion battery adhesives, and highbarrier materials. There was a certain research foundation for catalysts for the catalytic cracking of 1,1,2-trichloroethane. The different acidities and alkalinities of catalysts corresponded to different product distributions. Overall, there had been extensive research on the distribution of three isomeric products, but there were few reports on the study of other residual products, which hindered further understanding of the reaction mechanism. Therefore, it was necessary to study the in situ reaction process, which could examine the real-time catalytic performance of the catalysts and reveal the mechanism of the residual reactions. Mass spectrometry was used to study the residual products such as chloroacetylene and vinyl chloride generated by the system. In this paper, the product changes of the 1,1,2-trichloroethane in situ catalytic cracking reaction during the heating process were investigated. The results indicated that alumina-supported cesium-based catalysts had stronger selectivity for chloroacetylene, up to 10.46%, while alumina-supported barium-based catalysts had stronger selectivity for vinyl chloride, up to 3.86%. Cesium-based catalysts would lower the energy barrier for reactions to occur, allowing dichloroethylene, chloroacetylene, and vinyl chloride to form at lower temperatures. The generation temperature of dichloroethylene, chloroacetylene, and vinyl chloride in barium-based catalysts was higher. The experimental results revealed the changes in functional groups and product distribution of different catalysts during the in situ heating process, providing a theoretical basis for further catalyst redesign and inhibition of residual reactions.

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Section: Resultsmentioning

confidence: 99%

In Situ Reaction and Mass Spectrometry-Combined Technology for the Catalytic Performance of Cs/Al₂O₃ and Ba/Al₂O₃ in the Dehydrochlorination Reaction of 1,1,2-Trichloroethane

Shen,

Pan,

et al. 2024

Ind. Eng. Chem. Res.

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“…The isomerization of 3,4-DABE (12) also proceeds with Pt catalysts. [14] Pt catalysts were prepared using an impregnation method, but the activity of the catalysts varied considerably depending on the precursor used. For example, when H 2 PtCl 6 • 6H 2 O was used as a precursor, isomer (13) was obtained in 52 % yield, but when Pt(acac) 2 (acac:4-oxopent-2en-2-olate) and Pt(NH 3 ) 4 (NO 3 ) 2 were used as precursors, the reaction hardly proceeded (Table 2, entries 1-3).…”

Section: Pt/ceo 2 With Residual Chloride As Reusable Catalysts For Al...mentioning

confidence: 99%

Supported Noble Metal Catalysts and Adsorbents with Soft Lewis Acid Functions

Murayama

Huang

Yamamoto

et al. 2023

The Chemical Record

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Heterogeneous noble metal catalysts exhibit various functions. Although their redox functions have been extensively studied, we focused on their soft Lewis acid functions. Supported Au, Pt, and Pd catalysts electrophilically attack the π‐electrons of soft bases such as alkynes, alkenes, and aromatic compounds to perform addition and substitution reactions. Hydroamination, intramolecular cyclization of alkynyl carboxylic acids, isomerization of allylic esters, vinyl exchange reactions, Wacker oxidation, and oxidative homocoupling of aromatics are introduced based on a discussion of the active species and reaction mechanisms. Furthermore, the adsorption of sulfur compounds, which are soft bases, onto the supported AuNPs is discussed. The adsorption and removal of 1,3‐dimethyltrisulfane (DMTS), which is the compound responsible for the stale odor of “hine‐ka” in alcoholic beverages, particularly Japanese sake, is described.

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“…Some literatures had studied the catalytic splitting of 1,1,2-TCE to VDC or other reactions and achieved a series of results . Song et al elaborated the mechanism of 1,1,2-TCE catalytic splitting in depth and summarized the acid–base reaction mechanism of producing three kinds of DCE . Kong et al explained that the synergetic mechanism of metal and hydrogen chloride led to catalyst deactivation, which was considered as a kind of catalyst deactivation mechanism.…”

Section: Introductionmentioning

confidence: 99%

Catalyst Deactivation Process in 1,1,2-TCE Catalytic Dehydrochlorination Reaction

Ge,

Zhao,

Yuan

et al. 2024

Ind. Eng. Chem. Res.

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The heterogeneous catalytic splitting reaction of 1,1,2trichloroethane (1,1,2-TCE) was designed to study the process of catalyst deactivation. The results showed that the conversion of 1,1,2-TCE decreased from 51.34 to 44.01%, while the selectivity of vinylidene chloride decreased from 65.12 to 61.77% (260 °C, 8h), which indicated a decrease in catalyst activity. Solid-phase microextraction gas chromatography−mass spectrometry characterization was performed to confirm species on the surface of the spent catalyst. Density functional theory calculations revealed the essence of 1,1,2-TCE splitting to produce different products, and then a possible reaction network was proposed. Tandem side reactions occurred to generate chloroacetylene, which was an unstable species. Chloroacetylene selfpolymerized to form dichlorobutadiene and further polymerized to form aromatic compounds. The coke deposition precursors agglomerated on the surface of the active component, leading to catalyst deactivation. These conclusions explained the deactivation of the catalyst during 1,1,2-TCE dehydrochlorination, thus providing a theoretical basis for further research on methods to inhibit deactivation. Breaking through the key problem of catalyst deactivation would make it possible to replace the saponification reaction with catalytic dehydrochlorination in industry.

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Investigation of reusability and deactivation mechanism of supported platinum catalysts in the practical isomerization of allylic esters

Cited by 6 publications

References 23 publications

In Situ Reaction and Mass Spectrometry-Combined Technology for the Catalytic Performance of Cs/Al₂O₃ and Ba/Al₂O₃ in the Dehydrochlorination Reaction of 1,1,2-Trichloroethane

In Situ Reaction and Mass Spectrometry-Combined Technology for the Catalytic Performance of Cs/Al₂O₃ and Ba/Al₂O₃ in the Dehydrochlorination Reaction of 1,1,2-Trichloroethane

Supported Noble Metal Catalysts and Adsorbents with Soft Lewis Acid Functions

Catalyst Deactivation Process in 1,1,2-TCE Catalytic Dehydrochlorination Reaction

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Investigation of reusability and deactivation mechanism of supported platinum catalysts in the practical isomerization of allylic esters

Cited by 6 publications

References 23 publications

In Situ Reaction and Mass Spectrometry-Combined Technology for the Catalytic Performance of Cs/Al2O3 and Ba/Al2O3 in the Dehydrochlorination Reaction of 1,1,2-Trichloroethane

In Situ Reaction and Mass Spectrometry-Combined Technology for the Catalytic Performance of Cs/Al2O3 and Ba/Al2O3 in the Dehydrochlorination Reaction of 1,1,2-Trichloroethane

Supported Noble Metal Catalysts and Adsorbents with Soft Lewis Acid Functions

Catalyst Deactivation Process in 1,1,2-TCE Catalytic Dehydrochlorination Reaction

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In Situ Reaction and Mass Spectrometry-Combined Technology for the Catalytic Performance of Cs/Al₂O₃ and Ba/Al₂O₃ in the Dehydrochlorination Reaction of 1,1,2-Trichloroethane

In Situ Reaction and Mass Spectrometry-Combined Technology for the Catalytic Performance of Cs/Al₂O₃ and Ba/Al₂O₃ in the Dehydrochlorination Reaction of 1,1,2-Trichloroethane