Kinetics of 2-Methylfuran Acylation with Fatty Acid Anhydrides for Biorenewable Surfactants

Ankita V. Naik; Kristeen E. Joseph; Manish Shetty; M. Alexander Ardagh; Paul J. Dauenhauer

doi:10.1021/acssuschemeng.0c06847

Kinetics of 2-Methylfuran Acylation with Fatty Acid Anhydrides for Biorenewable Surfactants

Ankita V. Naik, Kristeen E. Joseph, Manish Shetty, M. Alexander Ardagh, Paul J. Dauenhauer

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

8 Scopus citations

Abstract

Friedel-Crafts acylation using long-chain fatty acid derivatives and biomass-derived furans is the key reaction to produce "alkyl furan ketones", an important precursor for biorenewable oleo-furan surfactants. In this work, the steady-state acylation kinetics and reaction mechanism were investigated using a model system of 2-methylfuran and n-octanoic anhydride in a fixed-bed tubular reactor using Al-MCM-41, a mesoporous aluminosilicate. An apparent activation energy (15.5 ± 1.4 kcal mol-1) was obtained for the formation of the acylated product, 2-octanoyl-5-methylfuran (2O5MF), for a temperature range of 348-408 K. The apparent reaction rate orders were â0.6 and â0.5 in the 2-methylfuran and anhydride concentrations, respectively, while near-zero apparent rate orders were measured in the product concentrations, indicating negligible product inhibition. An Eley-Rideal catalytic acylation mechanism was proposed to explain the experimentally observed apparent rate orders.

Original language	English (US)
Pages (from-to)	18616-18625
Number of pages	10
Journal	ACS Sustainable Chemistry and Engineering
Volume	8
Issue number	50
DOIs	https://doi.org/10.1021/acssuschemeng.0c06847
State	Published - Dec 21 2020
Externally published	Yes

Bibliographical note

Funding Information:
We acknowledge the financial support of the Catalysis Center for Energy Innovation, a U.S. Department of Energy—Energy Frontier Research Center under Grant DE-SC0001004. Parts of this work were carried out in the Characterization Facility (CharFac) at the University of Minnesota and the Minnesota NMR Center. The authors acknowledge Dr. Hanseung Lee at CharFac for performing the scanning electron microscopy experiments and Dr. Gopinath Tata at the NMR Centre for performing the solid-state NMR experiment. The authors also thank ChoongSze Lee and Dr. Matheus Dorneles De Mello for help with Ar physisorption.

Publisher Copyright:
© 2020 American Chemical Society.

Keywords

Al-MCM-41
acylation
biomass
chemical kinetics
oleo-furan surfactants
reaction mechanism

Access

10.1021/acssuschemeng.0c06847

OpenUrl availability

Full text

Cite this

@article{2c6d8bbfded84ee5a95eb1a08b256317,

title = "Kinetics of 2-Methylfuran Acylation with Fatty Acid Anhydrides for Biorenewable Surfactants",

abstract = "Friedel-Crafts acylation using long-chain fatty acid derivatives and biomass-derived furans is the key reaction to produce {"}alkyl furan ketones{"}, an important precursor for biorenewable oleo-furan surfactants. In this work, the steady-state acylation kinetics and reaction mechanism were investigated using a model system of 2-methylfuran and n-octanoic anhydride in a fixed-bed tubular reactor using Al-MCM-41, a mesoporous aluminosilicate. An apparent activation energy (15.5 ± 1.4 kcal mol-1) was obtained for the formation of the acylated product, 2-octanoyl-5-methylfuran (2O5MF), for a temperature range of 348-408 K. The apparent reaction rate orders were {\^a}0.6 and {\^a}0.5 in the 2-methylfuran and anhydride concentrations, respectively, while near-zero apparent rate orders were measured in the product concentrations, indicating negligible product inhibition. An Eley-Rideal catalytic acylation mechanism was proposed to explain the experimentally observed apparent rate orders.",

keywords = "Al-MCM-41, acylation, biomass, chemical kinetics, oleo-furan surfactants, reaction mechanism",

author = "Naik, {Ankita V.} and Joseph, {Kristeen E.} and Manish Shetty and Ardagh, {M. Alexander} and Dauenhauer, {Paul J.}",

note = "Funding Information: We acknowledge the financial support of the Catalysis Center for Energy Innovation, a U.S. Department of Energy—Energy Frontier Research Center under Grant DE-SC0001004. Parts of this work were carried out in the Characterization Facility (CharFac) at the University of Minnesota and the Minnesota NMR Center. The authors acknowledge Dr. Hanseung Lee at CharFac for performing the scanning electron microscopy experiments and Dr. Gopinath Tata at the NMR Centre for performing the solid-state NMR experiment. The authors also thank ChoongSze Lee and Dr. Matheus Dorneles De Mello for help with Ar physisorption. Publisher Copyright: {\textcopyright} 2020 American Chemical Society.",

year = "2020",

month = dec,

day = "21",

doi = "10.1021/acssuschemeng.0c06847",

language = "English (US)",

volume = "8",

pages = "18616--18625",

journal = "ACS Sustainable Chemistry and Engineering",

issn = "2168-0485",

publisher = "American Chemical Society",

number = "50",

}

TY - JOUR

T1 - Kinetics of 2-Methylfuran Acylation with Fatty Acid Anhydrides for Biorenewable Surfactants

AU - Naik, Ankita V.

AU - Joseph, Kristeen E.

AU - Shetty, Manish

AU - Ardagh, M. Alexander

AU - Dauenhauer, Paul J.

N1 - Funding Information: We acknowledge the financial support of the Catalysis Center for Energy Innovation, a U.S. Department of Energy—Energy Frontier Research Center under Grant DE-SC0001004. Parts of this work were carried out in the Characterization Facility (CharFac) at the University of Minnesota and the Minnesota NMR Center. The authors acknowledge Dr. Hanseung Lee at CharFac for performing the scanning electron microscopy experiments and Dr. Gopinath Tata at the NMR Centre for performing the solid-state NMR experiment. The authors also thank ChoongSze Lee and Dr. Matheus Dorneles De Mello for help with Ar physisorption. Publisher Copyright: © 2020 American Chemical Society.

PY - 2020/12/21

Y1 - 2020/12/21

N2 - Friedel-Crafts acylation using long-chain fatty acid derivatives and biomass-derived furans is the key reaction to produce "alkyl furan ketones", an important precursor for biorenewable oleo-furan surfactants. In this work, the steady-state acylation kinetics and reaction mechanism were investigated using a model system of 2-methylfuran and n-octanoic anhydride in a fixed-bed tubular reactor using Al-MCM-41, a mesoporous aluminosilicate. An apparent activation energy (15.5 ± 1.4 kcal mol-1) was obtained for the formation of the acylated product, 2-octanoyl-5-methylfuran (2O5MF), for a temperature range of 348-408 K. The apparent reaction rate orders were â0.6 and â0.5 in the 2-methylfuran and anhydride concentrations, respectively, while near-zero apparent rate orders were measured in the product concentrations, indicating negligible product inhibition. An Eley-Rideal catalytic acylation mechanism was proposed to explain the experimentally observed apparent rate orders.

AB - Friedel-Crafts acylation using long-chain fatty acid derivatives and biomass-derived furans is the key reaction to produce "alkyl furan ketones", an important precursor for biorenewable oleo-furan surfactants. In this work, the steady-state acylation kinetics and reaction mechanism were investigated using a model system of 2-methylfuran and n-octanoic anhydride in a fixed-bed tubular reactor using Al-MCM-41, a mesoporous aluminosilicate. An apparent activation energy (15.5 ± 1.4 kcal mol-1) was obtained for the formation of the acylated product, 2-octanoyl-5-methylfuran (2O5MF), for a temperature range of 348-408 K. The apparent reaction rate orders were â0.6 and â0.5 in the 2-methylfuran and anhydride concentrations, respectively, while near-zero apparent rate orders were measured in the product concentrations, indicating negligible product inhibition. An Eley-Rideal catalytic acylation mechanism was proposed to explain the experimentally observed apparent rate orders.

KW - Al-MCM-41

KW - acylation

KW - biomass

KW - chemical kinetics

KW - oleo-furan surfactants

KW - reaction mechanism

UR - http://www.scopus.com/inward/record.url?scp=85097778611&partnerID=8YFLogxK

UR - http://www.scopus.com/inward/citedby.url?scp=85097778611&partnerID=8YFLogxK

U2 - 10.1021/acssuschemeng.0c06847

DO - 10.1021/acssuschemeng.0c06847

M3 - Article

AN - SCOPUS:85097778611

SN - 2168-0485

VL - 8

SP - 18616

EP - 18625

JO - ACS Sustainable Chemistry and Engineering

JF - ACS Sustainable Chemistry and Engineering

IS - 50

ER -

Kinetics of 2-Methylfuran Acylation with Fatty Acid Anhydrides for Biorenewable Surfactants

Abstract

Bibliographical note

Keywords

Access

OpenUrl availability

Other files and links

Fingerprint

Cite this