Skeletal isomerisation of oleic acid over ferrierite: Influence of acid site number, accessibility and strength on activity and selectivity

Sophie C. C. Wiedemann; Ara Munoz-Murillo; R. Oord; Tanja van Bergen-Brenkman; Bas Wels; Pieter C. A. Bruijnincx; Bert M. Weckhuysen

doi:10.1016/j.jcat.2015.05.013

Skeletal isomerisation of oleic acid over ferrierite: Influence of acid site number, accessibility and strength on activity and selectivity

Sophie C. C. Wiedemann, Ara Munoz-Murillo, R. Oord, Tanja van Bergen-Brenkman, Bas Wels, Pieter C. A. Bruijnincx, Bert M. Weckhuysen^*

^*Corresponding author for this work

Croda Nederland

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

Abstract

Protonated ferrierite shows superior activity and selectivity in the liquid-phase isomerisation of linear unsaturated fatty acids to (mono-)branched-chain unsaturated fatty acids, (Mo)BUFA. This high selectivity is remarkable, as most of the interior surface of the zeolite is blocked already at the onset of reaction, limiting reaction to the pore mouth. A detailed study of the relationship between ferrierite acidity and performance is reported for five commercial catalysts; significant differences were found, independently of their bulk Si/AI ratios. Initial pore conversion correlates with Bronsted acidity in the 10-MR channels, as determined by adsorption/desorption of pyridine and FTIR. A low density of external acid sites reduces oligomerisation of fatty acids, while a high ratio of Bronsted to Lewis sites explains the observed high BUFA yield. The combination of FTIR with CO adsorption, and temperature-programmed desorption of NH3, confirms that the presence of strong but few Bronsted acid sites in the 10-MR channels increases selectivity to MoBUFA. (C) 2015 Elsevier Inc. All rights reserved.

Original language	English
Pages (from-to)	195-205
Number of pages	11
Journal	Journal of Catalysis
Volume	329
DOIs	https://doi.org/10.1016/j.jcat.2015.05.013
Publication status	Published - Sept 2015

Funding

The authors thank Croda for providing financial support. Tiny Verhoeven (Eindhoven University of Technology) is gratefully acknowledged for carrying out the XPS analyses. We would also like to thank Marjan Versluijs-Helder (Utrecht University) for performing the XRD and SEM analyses, and Arjan den Otter and dr. Jinbao Gao (Utrecht University) for helping with the physisorption measurements. Fouad Soulimani and dr. Hendrik van der Bij, both from Utrecht University, are thanked for support and advice in IR matters. Pascal Wijten (Utrecht University) is acknowledged for his assistance with the multi-autoclave operation. Finally, Negar Rashidi and Marvin Burger, both from Croda, contributed by carrying out a number of syntheses and analyses.

Keywords

Ferrierite
Alkyl isomerisation
Branched-chain unsaturated fatty acids
Pore-mouth catalysis
N-BUTENE ISOMERIZATION
CATALYTIC PERFORMANCE
CARBONACEOUS DEPOSITS
HFER ZEOLITES
SI/AL RATIO
FATTY-ACIDS
DEACTIVATION
ISOBUTENE
PYRIDINE
ISOMERS

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10.1016/j.jcat.2015.05.013

1-s2.0-S0021951715001608-mainFinal published version, 1.38 MBLicence: Taverne

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title = "Skeletal isomerisation of oleic acid over ferrierite: Influence of acid site number, accessibility and strength on activity and selectivity",

abstract = "Protonated ferrierite shows superior activity and selectivity in the liquid-phase isomerisation of linear unsaturated fatty acids to (mono-)branched-chain unsaturated fatty acids, (Mo)BUFA. This high selectivity is remarkable, as most of the interior surface of the zeolite is blocked already at the onset of reaction, limiting reaction to the pore mouth. A detailed study of the relationship between ferrierite acidity and performance is reported for five commercial catalysts; significant differences were found, independently of their bulk Si/AI ratios. Initial pore conversion correlates with Bronsted acidity in the 10-MR channels, as determined by adsorption/desorption of pyridine and FTIR. A low density of external acid sites reduces oligomerisation of fatty acids, while a high ratio of Bronsted to Lewis sites explains the observed high BUFA yield. The combination of FTIR with CO adsorption, and temperature-programmed desorption of NH3, confirms that the presence of strong but few Bronsted acid sites in the 10-MR channels increases selectivity to MoBUFA. (C) 2015 Elsevier Inc. All rights reserved.",

keywords = "Ferrierite, Alkyl isomerisation, Branched-chain unsaturated fatty acids, Pore-mouth catalysis, N-BUTENE ISOMERIZATION, CATALYTIC PERFORMANCE, CARBONACEOUS DEPOSITS, HFER ZEOLITES, SI/AL RATIO, FATTY-ACIDS, DEACTIVATION, ISOBUTENE, PYRIDINE, ISOMERS",

author = "Wiedemann, {Sophie C. C.} and Ara Munoz-Murillo and R. Oord and {van Bergen-Brenkman}, Tanja and Bas Wels and Bruijnincx, {Pieter C. A.} and Weckhuysen, {Bert M.}",

year = "2015",

month = sep,

doi = "10.1016/j.jcat.2015.05.013",

language = "English",

volume = "329",

pages = "195--205",

journal = "Journal of Catalysis",

issn = "0021-9517",

publisher = "Academic Press Inc.",

}

TY - JOUR

T1 - Skeletal isomerisation of oleic acid over ferrierite

T2 - Influence of acid site number, accessibility and strength on activity and selectivity

AU - Wiedemann, Sophie C. C.

AU - Munoz-Murillo, Ara

AU - Oord, R.

AU - van Bergen-Brenkman, Tanja

AU - Wels, Bas

AU - Bruijnincx, Pieter C. A.

AU - Weckhuysen, Bert M.

PY - 2015/9

Y1 - 2015/9

N2 - Protonated ferrierite shows superior activity and selectivity in the liquid-phase isomerisation of linear unsaturated fatty acids to (mono-)branched-chain unsaturated fatty acids, (Mo)BUFA. This high selectivity is remarkable, as most of the interior surface of the zeolite is blocked already at the onset of reaction, limiting reaction to the pore mouth. A detailed study of the relationship between ferrierite acidity and performance is reported for five commercial catalysts; significant differences were found, independently of their bulk Si/AI ratios. Initial pore conversion correlates with Bronsted acidity in the 10-MR channels, as determined by adsorption/desorption of pyridine and FTIR. A low density of external acid sites reduces oligomerisation of fatty acids, while a high ratio of Bronsted to Lewis sites explains the observed high BUFA yield. The combination of FTIR with CO adsorption, and temperature-programmed desorption of NH3, confirms that the presence of strong but few Bronsted acid sites in the 10-MR channels increases selectivity to MoBUFA. (C) 2015 Elsevier Inc. All rights reserved.

AB - Protonated ferrierite shows superior activity and selectivity in the liquid-phase isomerisation of linear unsaturated fatty acids to (mono-)branched-chain unsaturated fatty acids, (Mo)BUFA. This high selectivity is remarkable, as most of the interior surface of the zeolite is blocked already at the onset of reaction, limiting reaction to the pore mouth. A detailed study of the relationship between ferrierite acidity and performance is reported for five commercial catalysts; significant differences were found, independently of their bulk Si/AI ratios. Initial pore conversion correlates with Bronsted acidity in the 10-MR channels, as determined by adsorption/desorption of pyridine and FTIR. A low density of external acid sites reduces oligomerisation of fatty acids, while a high ratio of Bronsted to Lewis sites explains the observed high BUFA yield. The combination of FTIR with CO adsorption, and temperature-programmed desorption of NH3, confirms that the presence of strong but few Bronsted acid sites in the 10-MR channels increases selectivity to MoBUFA. (C) 2015 Elsevier Inc. All rights reserved.

KW - Ferrierite

KW - Alkyl isomerisation

KW - Branched-chain unsaturated fatty acids

KW - Pore-mouth catalysis

KW - N-BUTENE ISOMERIZATION

KW - CATALYTIC PERFORMANCE

KW - CARBONACEOUS DEPOSITS

KW - HFER ZEOLITES

KW - SI/AL RATIO

KW - FATTY-ACIDS

KW - DEACTIVATION

KW - ISOBUTENE

KW - PYRIDINE

KW - ISOMERS

U2 - 10.1016/j.jcat.2015.05.013

DO - 10.1016/j.jcat.2015.05.013

M3 - Article

SN - 0021-9517

VL - 329

SP - 195

EP - 205

JO - Journal of Catalysis

JF - Journal of Catalysis

ER -

Skeletal isomerisation of oleic acid over ferrierite: Influence of acid site number, accessibility and strength on activity and selectivity

Abstract

Funding

Keywords

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