The physicochemical and catalytic properties of clay extrudates in cyclization of citronellal

Zuzana Vajglová; Irina L. Simakova; Kari Eränen; Päivi Mäki-Arvela; Narendra Kumar; Markus Peurla; Stiina Tolvanen; Alexander Efimov; Leena Hupa; Jouko Peltonen; Dmitry Yu Murzin

doi:10.1016/j.apcata.2021.118426

The physicochemical and catalytic properties of clay extrudates in cyclization of citronellal

Zuzana Vajglová, Irina L. Simakova, Kari Eränen, Päivi Mäki-Arvela, Narendra Kumar, Markus Peurla, Stiina Tolvanen, Alexander Efimov, Leena Hupa, Jouko Peltonen, Dmitry Yu Murzin^*

^*Corresponding author for this work

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

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Abstract

Four clay materials, namely, bentonite, bleaching earth, attapulgite and sepiolite, were shaped into the cylindrical body by extrusion. Clays were characterized in depth by TEM, SEM-EDX, N₂ physisorption, pyridine FTIR, pH measurements, contact angle measurements, ²⁷Al MAS NMR, and the crush test. Catalytic properties were investigated in the citronellal cyclization as a model reaction. The reaction was performed in the trickle-bed reactor at 70 °C, 10 bar of Ar with 0.086 M initial citronellal concentration in cyclohexane. The best results were obtained over attapulgite with isopulegols yield of 24% and stereoselectivity to the desired isopulegol isomer of 61%. Attapulgite had the highest meso-to-micropore volume ratio, the highest basicity, a low Brønsted-to-Lewis acid sites ratio, and the lowest amount of Brønsted acid sites compared to other extrudates. In addition, same clay exhibited the highest mechanical strength of extrudates.

Original language	English
Article number	118426
Journal	Applied Catalysis A: General
Volume	629
Early online date	9 Nov 2021
DOIs	https://doi.org/10.1016/j.apcata.2021.118426
Publication status	Published - 5 Jan 2022
MoE publication type	A1 Journal article-refereed

Keywords

Attapulgite
Bentonite
Citronellal cyclization
Clay
Extrudates
Palygorskite
Sepiolite

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10.1016/j.apcata.2021.118426Licence: CC BY

1-s2.0-S0926860X21004403-mainFinal published version, 2.96 MBLicence: CC BY

https://urn.fi/URN:NBN:fi-fe2023030329314

Cite this

@article{87bc50f577234601b9dc6ce6b9c772fa,

title = "The physicochemical and catalytic properties of clay extrudates in cyclization of citronellal",

abstract = "Four clay materials, namely, bentonite, bleaching earth, attapulgite and sepiolite, were shaped into the cylindrical body by extrusion. Clays were characterized in depth by TEM, SEM-EDX, N2 physisorption, pyridine FTIR, pH measurements, contact angle measurements, 27Al MAS NMR, and the crush test. Catalytic properties were investigated in the citronellal cyclization as a model reaction. The reaction was performed in the trickle-bed reactor at 70 °C, 10 bar of Ar with 0.086 M initial citronellal concentration in cyclohexane. The best results were obtained over attapulgite with isopulegols yield of 24% and stereoselectivity to the desired isopulegol isomer of 61%. Attapulgite had the highest meso-to-micropore volume ratio, the highest basicity, a low Br{\o}nsted-to-Lewis acid sites ratio, and the lowest amount of Br{\o}nsted acid sites compared to other extrudates. In addition, same clay exhibited the highest mechanical strength of extrudates.",

keywords = "Attapulgite, Bentonite, Citronellal cyclization, Clay, Extrudates, Palygorskite, Sepiolite",

author = "Zuzana Vajglov{\'a} and Simakova, {Irina L.} and Kari Er{\"a}nen and P{\"a}ivi M{\"a}ki-Arvela and Narendra Kumar and Markus Peurla and Stiina Tolvanen and Alexander Efimov and Leena Hupa and Jouko Peltonen and Murzin, {Dmitry Yu}",

note = "Funding Information: The authors are grateful to Academy of Finland for funding through the project: Synthesis of spatially controlled catalysts with superior performance. Electron microscopy samples were processed and analyzed at the Electron Microscopy Laboratory, Institute of Biomedicine, University of Turku, which receives financial support from Biocenter Finland . The authors are grateful to Mark Martinez-Klimov for the pH measurements. I.S. is grateful for the support from the Ministry of Science and Higher Education of the Russian Federation , under the governmental order for Boreskov Institute of Catalysis (Project No. AAAAA21-121011390055-8 ). Publisher Copyright: {\textcopyright} 2021 The Authors",

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doi = "10.1016/j.apcata.2021.118426",

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T1 - The physicochemical and catalytic properties of clay extrudates in cyclization of citronellal

AU - Vajglová, Zuzana

AU - Simakova, Irina L.

AU - Eränen, Kari

AU - Mäki-Arvela, Päivi

AU - Kumar, Narendra

AU - Peurla, Markus

AU - Tolvanen, Stiina

AU - Efimov, Alexander

AU - Hupa, Leena

AU - Peltonen, Jouko

AU - Murzin, Dmitry Yu

N1 - Funding Information: The authors are grateful to Academy of Finland for funding through the project: Synthesis of spatially controlled catalysts with superior performance. Electron microscopy samples were processed and analyzed at the Electron Microscopy Laboratory, Institute of Biomedicine, University of Turku, which receives financial support from Biocenter Finland . The authors are grateful to Mark Martinez-Klimov for the pH measurements. I.S. is grateful for the support from the Ministry of Science and Higher Education of the Russian Federation , under the governmental order for Boreskov Institute of Catalysis (Project No. AAAAA21-121011390055-8 ). Publisher Copyright: © 2021 The Authors

PY - 2022/1/5

Y1 - 2022/1/5

N2 - Four clay materials, namely, bentonite, bleaching earth, attapulgite and sepiolite, were shaped into the cylindrical body by extrusion. Clays were characterized in depth by TEM, SEM-EDX, N2 physisorption, pyridine FTIR, pH measurements, contact angle measurements, 27Al MAS NMR, and the crush test. Catalytic properties were investigated in the citronellal cyclization as a model reaction. The reaction was performed in the trickle-bed reactor at 70 °C, 10 bar of Ar with 0.086 M initial citronellal concentration in cyclohexane. The best results were obtained over attapulgite with isopulegols yield of 24% and stereoselectivity to the desired isopulegol isomer of 61%. Attapulgite had the highest meso-to-micropore volume ratio, the highest basicity, a low Brønsted-to-Lewis acid sites ratio, and the lowest amount of Brønsted acid sites compared to other extrudates. In addition, same clay exhibited the highest mechanical strength of extrudates.

AB - Four clay materials, namely, bentonite, bleaching earth, attapulgite and sepiolite, were shaped into the cylindrical body by extrusion. Clays were characterized in depth by TEM, SEM-EDX, N2 physisorption, pyridine FTIR, pH measurements, contact angle measurements, 27Al MAS NMR, and the crush test. Catalytic properties were investigated in the citronellal cyclization as a model reaction. The reaction was performed in the trickle-bed reactor at 70 °C, 10 bar of Ar with 0.086 M initial citronellal concentration in cyclohexane. The best results were obtained over attapulgite with isopulegols yield of 24% and stereoselectivity to the desired isopulegol isomer of 61%. Attapulgite had the highest meso-to-micropore volume ratio, the highest basicity, a low Brønsted-to-Lewis acid sites ratio, and the lowest amount of Brønsted acid sites compared to other extrudates. In addition, same clay exhibited the highest mechanical strength of extrudates.

KW - Attapulgite

KW - Bentonite

KW - Citronellal cyclization

KW - Clay

KW - Extrudates

KW - Palygorskite

KW - Sepiolite

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U2 - 10.1016/j.apcata.2021.118426

DO - 10.1016/j.apcata.2021.118426

M3 - Article

AN - SCOPUS:85118892091

SN - 0926-860X

VL - 629

JO - Applied Catalysis A: General

JF - Applied Catalysis A: General

M1 - 118426

ER -

The physicochemical and catalytic properties of clay extrudates in cyclization of citronellal

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The physicochemical and catalytic properties of clay extrudates in cyclization of citronellal

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