Process intensification of alkynol semihydrogenation in a tube reactor coated with a Pd/ZnO catalyst

Nikolay Cherkasov; Yang Bai; Evgeny Rebrov

doi:10.3390/catal7120358

Process intensification of alkynol semihydrogenation in a tube reactor coated with a Pd/ZnO catalyst

Nikolay Cherkasov
, Yang Bai
, Evgeny Rebrov^*

^*Corresponding author for this work

University of Warwick
Stoli Catalysts Ltd.
Tver State Technical University

Research output: Contribution to journal › Article › peer-review

23 Citations (Scopus)

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Abstract

Semihydrogenation of 2-methyl-3-butyn-2-ol (MBY) was studied in a 5 m tube reactor wall-coated with a 5 wt % Pd/ZnO catalyst. The system allowed for the excellent selectivity towards the intermediate alkene of 97.8 ± 0.2% at an ambient H ₂ pressure and a MBY conversion below 90%. The maximum alkene yield reached 94.6% under solvent-free conditions and 96.0% in a 30 vol % MBY aqueous solution. The reactor stability was studied for 80 h on stream with a deactivation rate of only 0.07% per hour. Such a low deactivation rate provides a continuous operation of one month with only a two-fold decrease in catalyst activity and a metal leaching below 1 parts per billion (ppb). The excellent turn-over numbers (TON) of above 10 ⁵ illustrates a very efficient utilisation of the noble metal inside catalyst-coated tube reactors. When compared to batch operation at 70 °C, the reaction rate in flow reactor can be increased by eight times at a higher reaction temperature, keeping the same product decomposition of about 1% in both cases.

Original language	English
Article number	358
Journal	Catalysts
Volume	7
Issue number	12
DOIs	https://doi.org/10.3390/catal7120358
Publication status	Published - 25 Nov 2017

Bibliographical note

This is an open access article distributed under the Creative Commons Attribution License which permits unrestricted use, distribution, and reproduction in any medium, provided the original work is properly cited (CC BY 4.0).

Funding

The continuous flow hydrogenation allows for a significant process intensification by increasing The continuous flow hydrogenation allows for a significant process intensification by increasing the process temperature by 90 ◦°C above that used in a conventional batch reactor with a minimum the process temperature by 90 C above that used in a conventional batch reactor with a minimum substrate decomposition that does not exceed 1 mol% at the highest temperature studied. Under such substrate decomposition that does not exceed 1 mol% at the highest temperature studied. Under such conditions, the reaction rates increases by eight times without compromising the product selectivity, conditions, the reaction rates increases by eight times without compromising the product selectivity, allowing us to reduce the residence time from hours required in batch to seconds in flow. allowing us to reduce the residence time from hours required in batch to seconds in flow. Acknowledgments: The authors are grateful to Jonathan Strong for the ICP analysis, Guannan Hu for the XRD study of the Pd/ZnO catalyst. We also acknowledge the support of the European Research Council Proof of concept grant (project MiCARF 693739) and InnovateUK grant (900041) for funding this research. concept grant (project MiCARF 693739) and InnovateUK grant (900041) for funding this research. Author Contributions: N.C. and E.R. conceived and designed the experiments; Y.B. prepared the catalyst‐coated Author Contributions: N.C. and E.R. conceived and designed the experiments; Y.B. prepared the catalyst-coated tubes and performed the experiments; N.C. and Y.B. analysed the data; All the authors contributed to writing tthhee ppaappeerr..

Keywords

Acetylene
Ethylene
Flow chemistry
Hydrogenation
Lindlar
Palladium
Process intensification
Selectivity

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10.3390/catal7120358Licence: CC BY 3.0

Process Intensification of Alkynol SemihydrogenationFinal published version, 4.7 MBLicence: CC BY 3.0

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title = "Process intensification of alkynol semihydrogenation in a tube reactor coated with a Pd/ZnO catalyst",

abstract = " Semihydrogenation of 2-methyl-3-butyn-2-ol (MBY) was studied in a 5 m tube reactor wall-coated with a 5 wt \% Pd/ZnO catalyst. The system allowed for the excellent selectivity towards the intermediate alkene of 97.8 ± 0.2\% at an ambient H 2 pressure and a MBY conversion below 90\%. The maximum alkene yield reached 94.6\% under solvent-free conditions and 96.0\% in a 30 vol \% MBY aqueous solution. The reactor stability was studied for 80 h on stream with a deactivation rate of only 0.07\% per hour. Such a low deactivation rate provides a continuous operation of one month with only a two-fold decrease in catalyst activity and a metal leaching below 1 parts per billion (ppb). The excellent turn-over numbers (TON) of above 10 5 illustrates a very efficient utilisation of the noble metal inside catalyst-coated tube reactors. When compared to batch operation at 70 °C, the reaction rate in flow reactor can be increased by eight times at a higher reaction temperature, keeping the same product decomposition of about 1\% in both cases. ",

keywords = "Acetylene, Ethylene, Flow chemistry, Hydrogenation, Lindlar, Palladium, Process intensification, Selectivity",

author = "Nikolay Cherkasov and Yang Bai and Evgeny Rebrov",

note = "This is an open access article distributed under the Creative Commons Attribution License which permits unrestricted use, distribution, and reproduction in any medium, provided the original work is properly cited (CC BY 4.0).",

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doi = "10.3390/catal7120358",

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AU - Cherkasov, Nikolay

AU - Bai, Yang

AU - Rebrov, Evgeny

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PY - 2017/11/25

Y1 - 2017/11/25

N2 - Semihydrogenation of 2-methyl-3-butyn-2-ol (MBY) was studied in a 5 m tube reactor wall-coated with a 5 wt % Pd/ZnO catalyst. The system allowed for the excellent selectivity towards the intermediate alkene of 97.8 ± 0.2% at an ambient H 2 pressure and a MBY conversion below 90%. The maximum alkene yield reached 94.6% under solvent-free conditions and 96.0% in a 30 vol % MBY aqueous solution. The reactor stability was studied for 80 h on stream with a deactivation rate of only 0.07% per hour. Such a low deactivation rate provides a continuous operation of one month with only a two-fold decrease in catalyst activity and a metal leaching below 1 parts per billion (ppb). The excellent turn-over numbers (TON) of above 10 5 illustrates a very efficient utilisation of the noble metal inside catalyst-coated tube reactors. When compared to batch operation at 70 °C, the reaction rate in flow reactor can be increased by eight times at a higher reaction temperature, keeping the same product decomposition of about 1% in both cases.

AB - Semihydrogenation of 2-methyl-3-butyn-2-ol (MBY) was studied in a 5 m tube reactor wall-coated with a 5 wt % Pd/ZnO catalyst. The system allowed for the excellent selectivity towards the intermediate alkene of 97.8 ± 0.2% at an ambient H 2 pressure and a MBY conversion below 90%. The maximum alkene yield reached 94.6% under solvent-free conditions and 96.0% in a 30 vol % MBY aqueous solution. The reactor stability was studied for 80 h on stream with a deactivation rate of only 0.07% per hour. Such a low deactivation rate provides a continuous operation of one month with only a two-fold decrease in catalyst activity and a metal leaching below 1 parts per billion (ppb). The excellent turn-over numbers (TON) of above 10 5 illustrates a very efficient utilisation of the noble metal inside catalyst-coated tube reactors. When compared to batch operation at 70 °C, the reaction rate in flow reactor can be increased by eight times at a higher reaction temperature, keeping the same product decomposition of about 1% in both cases.

KW - Acetylene

KW - Ethylene

KW - Flow chemistry

KW - Hydrogenation

KW - Lindlar

KW - Palladium

KW - Process intensification

KW - Selectivity

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DO - 10.3390/catal7120358

M3 - Article

AN - SCOPUS:85036593975

SN - 2073-4344

VL - 7

JO - Catalysts

JF - Catalysts

IS - 12

M1 - 358

ER -

Process intensification of alkynol semihydrogenation in a tube reactor coated with a Pd/ZnO catalyst

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