Supported zirconium-based continuous-flow microreactor for effective Meerwein–Ponndorf–Verley reduction of cyclohexanone

Koreniuk, Agnieszka; Maresz, Katarzyna; Mrowiec-Białoń, Julita

doi:10.1016/j.catcom.2015.01.021

Cited by 15 publications

(10 citation statements)

References 27 publications

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“…The characterization of siliceous monolithic microreactors functionalized with zirconium species and their catalytic properties were described in our previous papers [17,18]. Kinetic studies were performed in the microreactors featured by the exceptionally low back-pressure.…”

Section: Resultsmentioning

confidence: 99%

“…Battilocchio et al reported the protocol for synthesizing various alcohols from aromatic and aliphatic carbonyl compounds using a packed-bed reactor filled with zirconium hydroxide catalyst [16]. In our previous works [17][18][19], we demonstrated excellent activity of zirconium-doped silica monolithic microreactors in cyclohexanone reductions and their improved performance compared with the batch process. It was shown that zirconium species terminated with propoxy ligands featured the highest activity in MPV reduction among various Lewis centers immobilized onto monoliths' surfaces used as reactive cores in microreactors.…”

Section: Introductionmentioning

confidence: 99%

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Selective Reduction of Ketones and Aldehydes in Continuous-Flow Microreactor—Kinetic Studies

2018

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Abstract:In this work, the kinetics of Meerwein-Ponndorf-Verley chemoselective reduction of carbonyl compounds was studied in monolithic continuous-flow microreactors. To the best of our knowledge, this is the first report on the MPV reaction kinetics performed in a flow process. The microreactors are a very attractive alternative to the batch reactors conventionally used in this process. The proposed micro-flow system for synthesis of unsaturated secondary alcohols proved to be very efficient and easily controlled. The microreactors had reactive cores made of zirconium-functionalized silica monoliths of excellent catalytic properties and flow characteristics. The catalytic experiments were carried out with the use of 2-butanol as a hydrogen donor. Herein, we present the kinetic parameters of cyclohexanone reduction in a flow reactor and data on the reaction rate for several important ketones and aldehydes. The lack of diffusion constraints in the microreactors was demonstrated. Our results were compared with those from other authors and demonstrate the great potential of microreactor applications in fine chemical and complex intermediate manufacturing.

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Section: Resultsmentioning

confidence: 99%

Section: Introductionmentioning

confidence: 99%

Selective Reduction of Ketones and Aldehydes in Continuous-Flow Microreactor—Kinetic Studies

2018

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“…The performance of MMRs doped with various Lewis acid centers has been extensively studied in the chemoselective Meerwein-Ponndorf-Verley (MPV) reduction of carbonyl compounds-a widespread route for the synthesis of unsaturated secondary alcohols, and the results have been presented in a series of articles (Koreniuk et al, 2015a;Ciemięga et al, 2017b;Ciemięga et al, 2018;Maresz et al, 2018;. Preliminary studies showed that modification of silica monoliths (M1 structure) with zirconium (IV) propoxide (Zr-Pr-MMR) resulted in the formation of zirconium complexes with mixed propoxy/hydroxyl ligands bound to the silica surface, which were much more catalytically active than silica-supported zirconia (Zr-MMR) (Koreniuk et al, 2015a). Moreover, the complexes appeared to be protected against hydrolysis during this modification as well as during the reactor operation.…”

Section: Monolithic Microchannel Reactors Functionalized With Transition Metalsmentioning

confidence: 99%

Catalytic Functionalized Structured Monolithic Micro-/Mesoreactors: Engineering, Properties, and Performance in Flow Synthesis: An Overview and Guidelines

et al. 2021

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In this review article, we first discussed the development of silica monoliths with hierarchical macro-/mesopore structure and their potential figures of merit as continuous-flow micro-/mesoreactors of up to 30 ml working volume. Making use of the flow hindrance of different pore structures seen from the Darcy law perspective, we discriminated four structures of the monoliths (M1–M4). We then summarized the most important results, mainly from our studies of continuous-flow structured monolithic reactors and rotating bed reactors (RBRs) filled with structured pellets, activated with various catalytic entities and enzymes. The results show that an increase in the flow rate and thus velocity in reactors activated with more conventional catalytic sites has no or a minor positive effect on the apparent reaction rate. On the contrary, in those with the most open structure (M1) and functionalized with enzymes, it could increase by more than two orders of magnitude even at low overpressures. The production systems worked stably for at least 200 h. To conclude, the synthetic system made of the hierarchically structured monoliths, or RBRs filled with structured catalytic pellets, lay the foundation for a new platform for the high-yield production of a wide variety of specialty chemicals, even on a multikilogram scale, in a safe and sustained manner.

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“…A theoretical possibility of heterogeneous catalytic process for obtaining the alcohol by the MPV mechanism is shown in [9,10]. Zeolites, mesoporous and micro-mesoporous silicates and aluminum oxide materials may prove to be promising catalysts for this process.…”

Section: Literature Review and Problem Statementmentioning

confidence: 99%

“…Such as the reaction of Baeyer-Villiger [7,11,12]; Meerwein-Ponndorf-Verley [13]; isomerization of hydrocarbons, obtained from biomass [9]. Such reactions involve molecules with a diameter of up to 10 Å.…”

Section: Literature Review and Problem Statementmentioning

confidence: 99%

Modeling the heterogeneous catalytic recovery processes of aldehydes and ketones

Skoretska

Beznosyk

2017

EEJET

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Досліджено дві гетерогенні каталітичні реакції віднов-лення за механізмом Меєрвейна-Понндорфа-Верлея -від-новлення анісового альдегіду з подальшою етерифікаці-єю та циклогексанону. Побудовано математичні моделі досліджених процесів. Проаналізовано активність трьох каталізаторів, за участі яких відбувалась реакція віднов-лення циклогексанону, та обрано для подальших розра-хунків найактивніший. Розраховано константи швидко-сті досліджених реакцій відновлення альдегідів та кетонів Ключові слова: механізм Меєрвейна-Понндорфа-Верлея, зворотна задача кінетики, константа швидкості, гетерогенний каталіз, цеоліти Исследованы две гетерогенные каталитические реак-ции восстановления по механизму Меервейна-Понндорфа-Верлея -восстановление анисового альдегида с после-дующей этерификацией и циклогексанона. Построены математические модели исследованных процессов. Проанализирована активность трех катализаторов, при участии которых происходила реакция восстановления циклогексанона, и выбран для дальнейших расчетов наи-более активный. Рассчитаны константы скорости иссле-дованных реакций восстановления альдегидов и кетонов Ключевые слова: механизм Меервейна-Понндорфа-Верлея, обратная задача кинетики, константа скорости, гетерогенный катализ, цеолиты UDC 544.4

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Supported zirconium-based continuous-flow microreactor for effective Meerwein–Ponndorf–Verley reduction of cyclohexanone

Cited by 15 publications

References 27 publications

Selective Reduction of Ketones and Aldehydes in Continuous-Flow Microreactor—Kinetic Studies

Selective Reduction of Ketones and Aldehydes in Continuous-Flow Microreactor—Kinetic Studies

Catalytic Functionalized Structured Monolithic Micro-/Mesoreactors: Engineering, Properties, and Performance in Flow Synthesis: An Overview and Guidelines

Modeling the heterogeneous catalytic recovery processes of aldehydes and ketones

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