Towards a deep desilication/dealumination of NU-10 zeolite: Shape-selectivity regulation

Clara Sá Couto, Patrícia Matias, Edgar T. Santos, Auguste Fernandes, Inês Graça, José M. Lopes*, Maria F. Ribeiro

*Corresponding author for this work

Research output: Contribution to journalArticle

9 Citations (Scopus)

Abstract

The present work was aimed at performing alkaline desilication of different severities, in order to generate a broad range of mesopore volumes within the framework of the intermediate pore size NU-10 zeolite and to evaluate both physicochemical and catalytic consequences. The shape-selective sensitive o-xylene isomerisation reaction was used as a characterisation method of zeolite pore modification. Thus, several NU-10 samples, with preserved crystallinity, were obtained by treatment of a microporous parent NU-10 sample with sodium hydroxide solutions of different concentrations (0.4-0.6 M), at several contact times (15, 30, 45, 60 and 120 min) and at 353 K. The characterisation by nitrogen adsorption allowed the evaluation of the micropore volumes of the samples and the mesopore volumes generated by desilication, as well as the external surface area. Toluene adsorption experiments were also performed, an important increase in the toluene adsorption capacity for increasing desilication levels being observed, except for the most severely modified samples. The sample treated at 0.6 M for 60 min revealed lower toluene retention, probably due to a higher level of extra-framework aluminium and silicon species remaining in the internal porosity. In the case of aluminium species, they were detected by 27Al NMR spectroscopy, which is also in agreement with the pronounced increase in the number of Lewis acid sites detected for the most severely treated samples. A slight decrease in the initial o-xylene isomerisation activity, at 673 K, was generally noticed as a consequence of desilication, and this can be related to a slight decrease in the concentration of protonated sites. Nevertheless, for intermediate-severity- treated samples, the activity per acid site increased significantly when compared with the parent zeolite, suggesting easier reactant accessibility. Furthermore, the para/meta-xylene product molar ratio decreased and, therefore, the zeolite shape selectivity, thus reinforcing the hypothesis of an extra space generation consequence on the catalytic properties.

Original languageEnglish
Pages (from-to)4190-4199
Number of pages10
JournalEuropean Journal of Inorganic Chemistry
Volume2012
Issue number26
Early online date31 Jul 2012
DOIs
Publication statusPublished - Sep 2012

Fingerprint

Zeolites
Toluene
Isomerization
Aluminum
Adsorption
Lewis Acids
Sodium Hydroxide
Silicon
Nuclear magnetic resonance spectroscopy
Pore size
Nitrogen
Porosity
Acids
Experiments
2-xylene

Keywords

  • Desilication
  • Isomerisation
  • Mesoporous materials
  • NU-10
  • Zeolites

ASJC Scopus subject areas

  • Inorganic Chemistry

Cite this

Sá Couto, C., Matias, P., Santos, E. T., Fernandes, A., Graça, I., Lopes, J. M., & Ribeiro, M. F. (2012). Towards a deep desilication/dealumination of NU-10 zeolite: Shape-selectivity regulation. European Journal of Inorganic Chemistry, 2012(26), 4190-4199. https://doi.org/10.1002/ejic.201200386

Towards a deep desilication/dealumination of NU-10 zeolite : Shape-selectivity regulation. / Sá Couto, Clara; Matias, Patrícia; Santos, Edgar T.; Fernandes, Auguste; Graça, Inês; Lopes, José M.; Ribeiro, Maria F.

In: European Journal of Inorganic Chemistry, Vol. 2012, No. 26, 09.2012, p. 4190-4199.

Research output: Contribution to journalArticle

Sá Couto, C, Matias, P, Santos, ET, Fernandes, A, Graça, I, Lopes, JM & Ribeiro, MF 2012, 'Towards a deep desilication/dealumination of NU-10 zeolite: Shape-selectivity regulation', European Journal of Inorganic Chemistry, vol. 2012, no. 26, pp. 4190-4199. https://doi.org/10.1002/ejic.201200386
Sá Couto, Clara ; Matias, Patrícia ; Santos, Edgar T. ; Fernandes, Auguste ; Graça, Inês ; Lopes, José M. ; Ribeiro, Maria F. / Towards a deep desilication/dealumination of NU-10 zeolite : Shape-selectivity regulation. In: European Journal of Inorganic Chemistry. 2012 ; Vol. 2012, No. 26. pp. 4190-4199.
@article{a289d2f2b78347b2b6cf004f74d624ea,
title = "Towards a deep desilication/dealumination of NU-10 zeolite: Shape-selectivity regulation",
abstract = "The present work was aimed at performing alkaline desilication of different severities, in order to generate a broad range of mesopore volumes within the framework of the intermediate pore size NU-10 zeolite and to evaluate both physicochemical and catalytic consequences. The shape-selective sensitive o-xylene isomerisation reaction was used as a characterisation method of zeolite pore modification. Thus, several NU-10 samples, with preserved crystallinity, were obtained by treatment of a microporous parent NU-10 sample with sodium hydroxide solutions of different concentrations (0.4-0.6 M), at several contact times (15, 30, 45, 60 and 120 min) and at 353 K. The characterisation by nitrogen adsorption allowed the evaluation of the micropore volumes of the samples and the mesopore volumes generated by desilication, as well as the external surface area. Toluene adsorption experiments were also performed, an important increase in the toluene adsorption capacity for increasing desilication levels being observed, except for the most severely modified samples. The sample treated at 0.6 M for 60 min revealed lower toluene retention, probably due to a higher level of extra-framework aluminium and silicon species remaining in the internal porosity. In the case of aluminium species, they were detected by 27Al NMR spectroscopy, which is also in agreement with the pronounced increase in the number of Lewis acid sites detected for the most severely treated samples. A slight decrease in the initial o-xylene isomerisation activity, at 673 K, was generally noticed as a consequence of desilication, and this can be related to a slight decrease in the concentration of protonated sites. Nevertheless, for intermediate-severity- treated samples, the activity per acid site increased significantly when compared with the parent zeolite, suggesting easier reactant accessibility. Furthermore, the para/meta-xylene product molar ratio decreased and, therefore, the zeolite shape selectivity, thus reinforcing the hypothesis of an extra space generation consequence on the catalytic properties.",
keywords = "Desilication, Isomerisation, Mesoporous materials, NU-10, Zeolites",
author = "{S{\'a} Couto}, Clara and Patr{\'i}cia Matias and Santos, {Edgar T.} and Auguste Fernandes and In{\^e}s Gra{\cc}a and Lopes, {Jos{\'e} M.} and Ribeiro, {Maria F.}",
year = "2012",
month = "9",
doi = "10.1002/ejic.201200386",
language = "English",
volume = "2012",
pages = "4190--4199",
journal = "European Journal of Inorganic Chemistry",
issn = "1434-1948",
publisher = "Wiley-VCH Verlag",
number = "26",

}

TY - JOUR

T1 - Towards a deep desilication/dealumination of NU-10 zeolite

T2 - Shape-selectivity regulation

AU - Sá Couto, Clara

AU - Matias, Patrícia

AU - Santos, Edgar T.

AU - Fernandes, Auguste

AU - Graça, Inês

AU - Lopes, José M.

AU - Ribeiro, Maria F.

PY - 2012/9

Y1 - 2012/9

N2 - The present work was aimed at performing alkaline desilication of different severities, in order to generate a broad range of mesopore volumes within the framework of the intermediate pore size NU-10 zeolite and to evaluate both physicochemical and catalytic consequences. The shape-selective sensitive o-xylene isomerisation reaction was used as a characterisation method of zeolite pore modification. Thus, several NU-10 samples, with preserved crystallinity, were obtained by treatment of a microporous parent NU-10 sample with sodium hydroxide solutions of different concentrations (0.4-0.6 M), at several contact times (15, 30, 45, 60 and 120 min) and at 353 K. The characterisation by nitrogen adsorption allowed the evaluation of the micropore volumes of the samples and the mesopore volumes generated by desilication, as well as the external surface area. Toluene adsorption experiments were also performed, an important increase in the toluene adsorption capacity for increasing desilication levels being observed, except for the most severely modified samples. The sample treated at 0.6 M for 60 min revealed lower toluene retention, probably due to a higher level of extra-framework aluminium and silicon species remaining in the internal porosity. In the case of aluminium species, they were detected by 27Al NMR spectroscopy, which is also in agreement with the pronounced increase in the number of Lewis acid sites detected for the most severely treated samples. A slight decrease in the initial o-xylene isomerisation activity, at 673 K, was generally noticed as a consequence of desilication, and this can be related to a slight decrease in the concentration of protonated sites. Nevertheless, for intermediate-severity- treated samples, the activity per acid site increased significantly when compared with the parent zeolite, suggesting easier reactant accessibility. Furthermore, the para/meta-xylene product molar ratio decreased and, therefore, the zeolite shape selectivity, thus reinforcing the hypothesis of an extra space generation consequence on the catalytic properties.

AB - The present work was aimed at performing alkaline desilication of different severities, in order to generate a broad range of mesopore volumes within the framework of the intermediate pore size NU-10 zeolite and to evaluate both physicochemical and catalytic consequences. The shape-selective sensitive o-xylene isomerisation reaction was used as a characterisation method of zeolite pore modification. Thus, several NU-10 samples, with preserved crystallinity, were obtained by treatment of a microporous parent NU-10 sample with sodium hydroxide solutions of different concentrations (0.4-0.6 M), at several contact times (15, 30, 45, 60 and 120 min) and at 353 K. The characterisation by nitrogen adsorption allowed the evaluation of the micropore volumes of the samples and the mesopore volumes generated by desilication, as well as the external surface area. Toluene adsorption experiments were also performed, an important increase in the toluene adsorption capacity for increasing desilication levels being observed, except for the most severely modified samples. The sample treated at 0.6 M for 60 min revealed lower toluene retention, probably due to a higher level of extra-framework aluminium and silicon species remaining in the internal porosity. In the case of aluminium species, they were detected by 27Al NMR spectroscopy, which is also in agreement with the pronounced increase in the number of Lewis acid sites detected for the most severely treated samples. A slight decrease in the initial o-xylene isomerisation activity, at 673 K, was generally noticed as a consequence of desilication, and this can be related to a slight decrease in the concentration of protonated sites. Nevertheless, for intermediate-severity- treated samples, the activity per acid site increased significantly when compared with the parent zeolite, suggesting easier reactant accessibility. Furthermore, the para/meta-xylene product molar ratio decreased and, therefore, the zeolite shape selectivity, thus reinforcing the hypothesis of an extra space generation consequence on the catalytic properties.

KW - Desilication

KW - Isomerisation

KW - Mesoporous materials

KW - NU-10

KW - Zeolites

UR - http://www.scopus.com/inward/record.url?scp=84865854828&partnerID=8YFLogxK

U2 - 10.1002/ejic.201200386

DO - 10.1002/ejic.201200386

M3 - Article

AN - SCOPUS:84865854828

VL - 2012

SP - 4190

EP - 4199

JO - European Journal of Inorganic Chemistry

JF - European Journal of Inorganic Chemistry

SN - 1434-1948

IS - 26

ER -