Improved Reactivity of Cellulose via Its Crystallinity Reduction by Nondissolving Pretreatment with an Ionic Liquid

Carlos A. Pena; Ana Soto; Alistair W.T. King; Héctor Rodríguez

doi:10.1021/acssuschemeng.8b06357

Improved Reactivity of Cellulose via Its Crystallinity Reduction by Nondissolving Pretreatment with an Ionic Liquid

Carlos A. Pena
, Ana Soto
, Alistair W.T. King
, Héctor Rodríguez^*

^*Corresponding author for this work

Not published at VTT

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

35 Citations (Scopus)

Abstract

The improvement of the reactivity of cellulose by means of an efficient pretreatment method is critical for the optimal valorization of this biorenewable polymer within a biorefinery context. In this work, a nondissolving procedure for the pretreatment of cellulose, based on the direct solid-liquid contact of cellulose with an ionic liquid, namely tetrabutylphosphonium acetate, or with its mixtures with water or dimethyl sulfoxide, was found to lead to an effective reduction of the cellulose crystallinity. Due to the nondissolving nature of the method, the cellulose thus pretreated can be simply recovered by filtration from the pretreatment fluid. The use of the molecular cosolvents, as compared to the use of the neat ionic liquid, results in a less viscous pretreatment fluid and also in a larger reduction of the cellulose crystallinity. An improvement in the reactivity of the pretreated cellulose was evidenced via the determination of the kinetics of an enzymatic hydrolysis. A relationship between this reaction kinetics and the degree of crystallinity of the cellulose was inferred: the lower the crystallinity, the faster the hydrolysis. The thermal stability and degree of polymerization of the pretreated cellulose samples were comparable or essentially unaltered with respect to the untreated cellulose.

Original language	English
Pages (from-to)	9164-9171
Number of pages	8
Journal	ACS Sustainable Chemistry and Engineering
Volume	7
Issue number	10
DOIs	https://doi.org/10.1021/acssuschemeng.8b06357
Publication status	Published - 20 May 2019
MoE publication type	A1 Journal article-refereed

Funding

The authors will be forever indebted to the figure of Kenneth R. Seddon, whose friendship and support was decisive in the development of ionic liquid research efforts at the University of Santiago de Compostela. The authors are grateful to Xunta de Galicia for support through project ED431B 2017/023 and the Galician Network of Ionic Liquids (ED431D 2017/06) and the CRETUS Strategic Partnership (ED431E 2018/01), cofunded by the European Regional Development Fund. The authors thank Dr. Thelmo A. Lu-Chau for advice and discussion on experimental issues. The use of RIAIDT-USC analytical facilities is also acknowledged.

Keywords

cellulose
crystallinity index
degree of polymerization
enzymatic hydrolysis
tetrabutylphosphonium

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10.1021/acssuschemeng.8b06357

Cite this

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title = "Improved Reactivity of Cellulose via Its Crystallinity Reduction by Nondissolving Pretreatment with an Ionic Liquid",

abstract = "The improvement of the reactivity of cellulose by means of an efficient pretreatment method is critical for the optimal valorization of this biorenewable polymer within a biorefinery context. In this work, a nondissolving procedure for the pretreatment of cellulose, based on the direct solid-liquid contact of cellulose with an ionic liquid, namely tetrabutylphosphonium acetate, or with its mixtures with water or dimethyl sulfoxide, was found to lead to an effective reduction of the cellulose crystallinity. Due to the nondissolving nature of the method, the cellulose thus pretreated can be simply recovered by filtration from the pretreatment fluid. The use of the molecular cosolvents, as compared to the use of the neat ionic liquid, results in a less viscous pretreatment fluid and also in a larger reduction of the cellulose crystallinity. An improvement in the reactivity of the pretreated cellulose was evidenced via the determination of the kinetics of an enzymatic hydrolysis. A relationship between this reaction kinetics and the degree of crystallinity of the cellulose was inferred: the lower the crystallinity, the faster the hydrolysis. The thermal stability and degree of polymerization of the pretreated cellulose samples were comparable or essentially unaltered with respect to the untreated cellulose.",

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author = "Pena, \{Carlos A.\} and Ana Soto and King, \{Alistair W.T.\} and H{\'e}ctor Rodr{\'i}guez",

note = "Funding Information: The authors will be forever indebted to the figure of Kenneth R. Seddon, whose friendship and support was decisive in the development of ionic liquid research efforts at the University of Santiago de Compostela. The authors are grateful to Xunta de Galicia for support through project ED431B 2017/023 and the Galician Network of Ionic Liquids (ED431D 2017/06) and the CRETUS Strategic Partnership (ED431E 2018/01), cofunded by the European Regional Development Fund. The authors thank Dr. Thelmo A. Lu-Chau for advice and discussion on experimental issues. The use of RIAIDT-USC analytical facilities is also acknowledged. Publisher Copyright: {\textcopyright} 2019 American Chemical Society.",

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N1 - Funding Information: The authors will be forever indebted to the figure of Kenneth R. Seddon, whose friendship and support was decisive in the development of ionic liquid research efforts at the University of Santiago de Compostela. The authors are grateful to Xunta de Galicia for support through project ED431B 2017/023 and the Galician Network of Ionic Liquids (ED431D 2017/06) and the CRETUS Strategic Partnership (ED431E 2018/01), cofunded by the European Regional Development Fund. The authors thank Dr. Thelmo A. Lu-Chau for advice and discussion on experimental issues. The use of RIAIDT-USC analytical facilities is also acknowledged. Publisher Copyright: © 2019 American Chemical Society.

PY - 2019/5/20

Y1 - 2019/5/20

N2 - The improvement of the reactivity of cellulose by means of an efficient pretreatment method is critical for the optimal valorization of this biorenewable polymer within a biorefinery context. In this work, a nondissolving procedure for the pretreatment of cellulose, based on the direct solid-liquid contact of cellulose with an ionic liquid, namely tetrabutylphosphonium acetate, or with its mixtures with water or dimethyl sulfoxide, was found to lead to an effective reduction of the cellulose crystallinity. Due to the nondissolving nature of the method, the cellulose thus pretreated can be simply recovered by filtration from the pretreatment fluid. The use of the molecular cosolvents, as compared to the use of the neat ionic liquid, results in a less viscous pretreatment fluid and also in a larger reduction of the cellulose crystallinity. An improvement in the reactivity of the pretreated cellulose was evidenced via the determination of the kinetics of an enzymatic hydrolysis. A relationship between this reaction kinetics and the degree of crystallinity of the cellulose was inferred: the lower the crystallinity, the faster the hydrolysis. The thermal stability and degree of polymerization of the pretreated cellulose samples were comparable or essentially unaltered with respect to the untreated cellulose.

AB - The improvement of the reactivity of cellulose by means of an efficient pretreatment method is critical for the optimal valorization of this biorenewable polymer within a biorefinery context. In this work, a nondissolving procedure for the pretreatment of cellulose, based on the direct solid-liquid contact of cellulose with an ionic liquid, namely tetrabutylphosphonium acetate, or with its mixtures with water or dimethyl sulfoxide, was found to lead to an effective reduction of the cellulose crystallinity. Due to the nondissolving nature of the method, the cellulose thus pretreated can be simply recovered by filtration from the pretreatment fluid. The use of the molecular cosolvents, as compared to the use of the neat ionic liquid, results in a less viscous pretreatment fluid and also in a larger reduction of the cellulose crystallinity. An improvement in the reactivity of the pretreated cellulose was evidenced via the determination of the kinetics of an enzymatic hydrolysis. A relationship between this reaction kinetics and the degree of crystallinity of the cellulose was inferred: the lower the crystallinity, the faster the hydrolysis. The thermal stability and degree of polymerization of the pretreated cellulose samples were comparable or essentially unaltered with respect to the untreated cellulose.

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KW - degree of polymerization

KW - enzymatic hydrolysis

KW - tetrabutylphosphonium

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IS - 10

ER -

Improved Reactivity of Cellulose via Its Crystallinity Reduction by Nondissolving Pretreatment with an Ionic Liquid

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Keywords

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