An examination of catalyst deactivation in p-chloronitrobenzene hydrogenation over supported gold

Fernando Cárdenas-Lizana, Xiaodong Wang, Daniel Lamey, Maoshuai Li, Mark A. Keane, Lioubov Kiwi-Minsker

Research output: Contribution to journalArticle

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Abstract

The stability of Au/Al2O3 in the continuous gas phase (423 K) hydrogenation of p-chloronitrobenzene (p-CNB) to p-chloroaniline (p-CAN) has been investigated over an inlet H2/p-CNB = 4–390, i.e. from close to stoichiometry to H2 far in excess. The catalyst (activated unused and spent) has been characterised with respect to specific surface area (SSA)/porosity, temperature programmed reduction (TPR), powder XRD, H2 chemisorption, STEM, XPS, elemental analysis and TGA–DSC measurements. Activation of Au/Al2O3 by TPR in hydrogen generated a narrow Au size distribution (1–8 nm, mean = 3.6 nm) with evidence (from XPS) of (support → metal) charge transfer to generate surface Auδ−. Exclusive p-CAN production was achieved under conditions of kinetic control, which were established by parameter estimation and experimental variation of contact time, catalyst particle size and p-CNB/catalyst ratio. A temporal decline in activity was observed that was more pronounced at H2/p-CNB ⩽39. The spent catalyst exhibited equivalent SSA/porosity, Au particle size (from STEM) and electronic character (from XPS) relative to activated unused Au/Al2O3. A significant carbon content (6.3% w/w) was determined from elemental analysis and confirmed by XPS and TGA–DSC. This carbon deposit hindered H2 chemisorption under reaction conditions, leading to suppressed hydrogenation activity. Catalyst regeneration by oxidative/reductive treatment resulted in a restoration of the initial hydrogenation activity, retaining exclusive selectivity to p-CAN.
Original languageEnglish
Pages (from-to) 695–704
Number of pages10
JournalChemical Engineering Journal
Volume255
Early online date28 Jun 2014
DOIs
Publication statusPublished - 1 Nov 2014

Fingerprint

Catalyst deactivation
Gold
Hydrogenation
X ray photoelectron spectroscopy
gold
catalyst
X-ray spectroscopy
Catalysts
Chemisorption
Specific surface area
Carbon
Porosity
Particle size
Catalyst regeneration
surface area
porosity
particle size
Chemical analysis
Stoichiometry
Powders

Keywords

  • selective gas phase hydrogenation
  • p-chloronitrobenzene
  • p-chloroaniline
  • Au/Al2O3
  • hydrogen partial pressure
  • catalyst deactivation and regeneration

Cite this

Cárdenas-Lizana, F., Wang, X., Lamey, D., Li, M., Keane, M. A., & Kiwi-Minsker, L. (2014). An examination of catalyst deactivation in p-chloronitrobenzene hydrogenation over supported gold. Chemical Engineering Journal, 255, 695–704. https://doi.org/10.1016/j.cej.2014.04.116

An examination of catalyst deactivation in p-chloronitrobenzene hydrogenation over supported gold. / Cárdenas-Lizana, Fernando; Wang, Xiaodong; Lamey, Daniel; Li, Maoshuai; Keane, Mark A.; Kiwi-Minsker, Lioubov.

In: Chemical Engineering Journal, Vol. 255, 01.11.2014, p. 695–704.

Research output: Contribution to journalArticle

Cárdenas-Lizana, F, Wang, X, Lamey, D, Li, M, Keane, MA & Kiwi-Minsker, L 2014, 'An examination of catalyst deactivation in p-chloronitrobenzene hydrogenation over supported gold', Chemical Engineering Journal, vol. 255, pp. 695–704. https://doi.org/10.1016/j.cej.2014.04.116
Cárdenas-Lizana, Fernando ; Wang, Xiaodong ; Lamey, Daniel ; Li, Maoshuai ; Keane, Mark A. ; Kiwi-Minsker, Lioubov. / An examination of catalyst deactivation in p-chloronitrobenzene hydrogenation over supported gold. In: Chemical Engineering Journal. 2014 ; Vol. 255. pp. 695–704.
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abstract = "The stability of Au/Al2O3 in the continuous gas phase (423 K) hydrogenation of p-chloronitrobenzene (p-CNB) to p-chloroaniline (p-CAN) has been investigated over an inlet H2/p-CNB = 4–390, i.e. from close to stoichiometry to H2 far in excess. The catalyst (activated unused and spent) has been characterised with respect to specific surface area (SSA)/porosity, temperature programmed reduction (TPR), powder XRD, H2 chemisorption, STEM, XPS, elemental analysis and TGA–DSC measurements. Activation of Au/Al2O3 by TPR in hydrogen generated a narrow Au size distribution (1–8 nm, mean = 3.6 nm) with evidence (from XPS) of (support → metal) charge transfer to generate surface Auδ−. Exclusive p-CAN production was achieved under conditions of kinetic control, which were established by parameter estimation and experimental variation of contact time, catalyst particle size and p-CNB/catalyst ratio. A temporal decline in activity was observed that was more pronounced at H2/p-CNB ⩽39. The spent catalyst exhibited equivalent SSA/porosity, Au particle size (from STEM) and electronic character (from XPS) relative to activated unused Au/Al2O3. A significant carbon content (6.3{\%} w/w) was determined from elemental analysis and confirmed by XPS and TGA–DSC. This carbon deposit hindered H2 chemisorption under reaction conditions, leading to suppressed hydrogenation activity. Catalyst regeneration by oxidative/reductive treatment resulted in a restoration of the initial hydrogenation activity, retaining exclusive selectivity to p-CAN.",
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N1 - Acknowledgments The authors are grateful to Jialin Yu, Oliver Beswick and Jean-Marc Bielser for their contribution to this work. Financial support from the Swiss National Science Foundation (Grant 200020-132522/1) and the Scottish Overseas Research Student Award Scheme (SORSAS) are acknowledged.

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N2 - The stability of Au/Al2O3 in the continuous gas phase (423 K) hydrogenation of p-chloronitrobenzene (p-CNB) to p-chloroaniline (p-CAN) has been investigated over an inlet H2/p-CNB = 4–390, i.e. from close to stoichiometry to H2 far in excess. The catalyst (activated unused and spent) has been characterised with respect to specific surface area (SSA)/porosity, temperature programmed reduction (TPR), powder XRD, H2 chemisorption, STEM, XPS, elemental analysis and TGA–DSC measurements. Activation of Au/Al2O3 by TPR in hydrogen generated a narrow Au size distribution (1–8 nm, mean = 3.6 nm) with evidence (from XPS) of (support → metal) charge transfer to generate surface Auδ−. Exclusive p-CAN production was achieved under conditions of kinetic control, which were established by parameter estimation and experimental variation of contact time, catalyst particle size and p-CNB/catalyst ratio. A temporal decline in activity was observed that was more pronounced at H2/p-CNB ⩽39. The spent catalyst exhibited equivalent SSA/porosity, Au particle size (from STEM) and electronic character (from XPS) relative to activated unused Au/Al2O3. A significant carbon content (6.3% w/w) was determined from elemental analysis and confirmed by XPS and TGA–DSC. This carbon deposit hindered H2 chemisorption under reaction conditions, leading to suppressed hydrogenation activity. Catalyst regeneration by oxidative/reductive treatment resulted in a restoration of the initial hydrogenation activity, retaining exclusive selectivity to p-CAN.

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KW - selective gas phase hydrogenation

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KW - p-chloroaniline

KW - Au/Al2O3

KW - hydrogen partial pressure

KW - catalyst deactivation and regeneration

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DO - 10.1016/j.cej.2014.04.116

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JO - Chemical Engineering Journal

JF - Chemical Engineering Journal

SN - 1385-8947

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