Esterification of Glycerol with Acetic Acid Using Nitrogen-Based Brønsted-Acidic Ionic Liquids

John Keogh, Manishkumar S. Tiwari, Haresh Manyar*

*Corresponding author for this work

Research output: Contribution to journalArticle

1 Citation (Scopus)

Abstract

Glycerol esterification with acetic acid produces a mixture of mono, di, and triacetins, which are commercially important value-added products with a wide range of industrial uses including their application as fuel-additives, thus contributing to environmental sustainability and economic viability of the biorefinery concept. Glycerol esterification with acetic acid was studied using a range of nitrogen-based Brønsted-acidic ionic liquids. Cost-effective and easily synthesized Brønsted-acidic ionic liquids based on alkyl-pyrrolidone and alkyl-amine cations were synthesized and characterized using 1H NMR spectroscopy. The catalytic activity of the Brønsted-acidic ionic liquids produced were investigated for the production of di and triacetin from glycerol and acetic acid. Amongst all ionic liquids evaluated in this study, N-methyl-2-pyrrolidinium hydrogen sulfate [H-NMP][HSO4] was found to be the most active and cost-effective catalyst. The effect of significant reaction parameters on selectivity to the trisubstituted product, triacetin, was modeled using a design of experiment (DoE) approach with a response surface methodology involving a central composite design. The esterification process was optimized to maximize the production of triacetin. Optimizing the process this way naturally leads to lower levels of mono and diacetin. Amongst the reaction parameters evaluated, temperature had the greatest influence on product selectivity, followed by the glycerol to acetic acid molar ratio, and the model also showed dependence on the synergistic interaction between the temperature and mole ratio. It is worth noting that agitation speed had minimal influence on product selectivity. Under optimized reaction conditions, >99% glycerol conversion was achieved with 42.3% selectivity to triacetin, and a combined di and triacetin selectivity of >95% within 1 h.

Original languageEnglish
Pages (from-to)17235-17243
Number of pages9
JournalIndustrial and Engineering Chemistry Research
Volume58
Issue number37
Early online date19 Aug 2019
DOIs
Publication statusPublished - 18 Sep 2019

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Triacetin
Ionic Liquids
Esterification
Glycerol
Ionic liquids
Acetic acid
Acetic Acid
Nitrogen
Fuel additives
Hydrogen
Pyrrolidinones
Design of experiments
Nuclear magnetic resonance spectroscopy
Costs
Sustainable development
Amines
Catalyst activity
Sulfates
Positive ions
Cations

Cite this

@article{1196c3af42c348a2a3c722dc6933f599,
title = "Esterification of Glycerol with Acetic Acid Using Nitrogen-Based Br{\o}nsted-Acidic Ionic Liquids",
abstract = "Glycerol esterification with acetic acid produces a mixture of mono, di, and triacetins, which are commercially important value-added products with a wide range of industrial uses including their application as fuel-additives, thus contributing to environmental sustainability and economic viability of the biorefinery concept. Glycerol esterification with acetic acid was studied using a range of nitrogen-based Br{\o}nsted-acidic ionic liquids. Cost-effective and easily synthesized Br{\o}nsted-acidic ionic liquids based on alkyl-pyrrolidone and alkyl-amine cations were synthesized and characterized using 1H NMR spectroscopy. The catalytic activity of the Br{\o}nsted-acidic ionic liquids produced were investigated for the production of di and triacetin from glycerol and acetic acid. Amongst all ionic liquids evaluated in this study, N-methyl-2-pyrrolidinium hydrogen sulfate [H-NMP][HSO4] was found to be the most active and cost-effective catalyst. The effect of significant reaction parameters on selectivity to the trisubstituted product, triacetin, was modeled using a design of experiment (DoE) approach with a response surface methodology involving a central composite design. The esterification process was optimized to maximize the production of triacetin. Optimizing the process this way naturally leads to lower levels of mono and diacetin. Amongst the reaction parameters evaluated, temperature had the greatest influence on product selectivity, followed by the glycerol to acetic acid molar ratio, and the model also showed dependence on the synergistic interaction between the temperature and mole ratio. It is worth noting that agitation speed had minimal influence on product selectivity. Under optimized reaction conditions, >99{\%} glycerol conversion was achieved with 42.3{\%} selectivity to triacetin, and a combined di and triacetin selectivity of >95{\%} within 1 h.",
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Esterification of Glycerol with Acetic Acid Using Nitrogen-Based Brønsted-Acidic Ionic Liquids. / Keogh, John; Tiwari, Manishkumar S.; Manyar, Haresh.

In: Industrial and Engineering Chemistry Research, Vol. 58, No. 37, 18.09.2019, p. 17235-17243.

Research output: Contribution to journalArticle

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AU - Keogh, John

AU - Tiwari, Manishkumar S.

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AB - Glycerol esterification with acetic acid produces a mixture of mono, di, and triacetins, which are commercially important value-added products with a wide range of industrial uses including their application as fuel-additives, thus contributing to environmental sustainability and economic viability of the biorefinery concept. Glycerol esterification with acetic acid was studied using a range of nitrogen-based Brønsted-acidic ionic liquids. Cost-effective and easily synthesized Brønsted-acidic ionic liquids based on alkyl-pyrrolidone and alkyl-amine cations were synthesized and characterized using 1H NMR spectroscopy. The catalytic activity of the Brønsted-acidic ionic liquids produced were investigated for the production of di and triacetin from glycerol and acetic acid. Amongst all ionic liquids evaluated in this study, N-methyl-2-pyrrolidinium hydrogen sulfate [H-NMP][HSO4] was found to be the most active and cost-effective catalyst. The effect of significant reaction parameters on selectivity to the trisubstituted product, triacetin, was modeled using a design of experiment (DoE) approach with a response surface methodology involving a central composite design. The esterification process was optimized to maximize the production of triacetin. Optimizing the process this way naturally leads to lower levels of mono and diacetin. Amongst the reaction parameters evaluated, temperature had the greatest influence on product selectivity, followed by the glycerol to acetic acid molar ratio, and the model also showed dependence on the synergistic interaction between the temperature and mole ratio. It is worth noting that agitation speed had minimal influence on product selectivity. Under optimized reaction conditions, >99% glycerol conversion was achieved with 42.3% selectivity to triacetin, and a combined di and triacetin selectivity of >95% within 1 h.

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