Solvent processing of cellulose for effective bioresource utilization

doi:10.1016/j.cogsc.2018.05.008

Current Opinion in Green and Sustainable Chemistry

Volume 14, December 2018, Pages 40-52

https://doi.org/10.1016/j.cogsc.2018.05.008 Get rights and content

Cellulose, the main constituent of plant biomass, is a unique stereoregular, chiral, biocompatible and reactive polymer that finds many applications. Despite the novel features of cellulose, its full potential as a functional polymer has yet to be realized in part because of the difficulty in dissolving cellulose. Non-derivatizing solvents for cellulose are reviewed here, with a focus on the better studied and more effective aqueous alkali (base) containing solvents, organic solvent systems, and ionic liquids. Recent advances are highlighted on cellulose-solvent interactions and on the mechanism and kinetics of semicrystalline cellulose dissolution. An improved fundamental understanding of molecular interactions (nanoscale), coupled with the biomass dissolution mechanism (microscopic level), can guide the rational selection and (macroscopic) optimization of solvent processing conditions. Opportunities abound for the translation of research fundamentals into the development of industrial solvent-based processes for the efficient production of high value-added polymers and chemicals from sustainable resources.

Introduction

This review is motivated by the substantial opportunities that solvent processing presents for the efficient utilization of cellulosic biomass, an abundant and renewable natural resource, toward the production of functional polymers, specialty chemicals, and biofuels. The recalcitrance of crystalline cellulose poses a severe bottleneck in the effective processing of biomass. Several approaches have been found useful for the “activation” of crystalline cellulose, however, many unanswered questions remain concerning the dissolution of cellulose at the molecular, mesoscopic, and macroscopic (process) levels ••1, ••2, ••3.

This review commences with an introduction to the unique features and structural complexities presented by cellulose, and the great potential that cellulosic biomass has for the production of valuable products. Non-derivatizing solvents for cellulose are discussed next, with a focus on the better studied and more effective aqueous alkali (base) containing solvents, organic solvent systems, and ionic liquids. Recent advances are then presented on the fundamental understanding of cellulose dissolution, with particular attention on cellulose-solvent interactions and on the mechanism and kinetics of semicrystalline cellulose dissolution.

The research findings highlighted here support the efficient production of high value-added polymers and chemicals from sustainable resources.

Section snippets

Motivation: processing of biomass to valuable products

The confluence of constrained petroleum supplies and increasing materials and energy demands by emerging economies exerts great pressure for the sustainable production of carbon-based chemicals and fuels. Plant biomass is a major, sustainable source of organic carbon. Government estimates suggest that the U.S., while still meeting its food, feed, and export demands, could sustainably produce 1.3 × 10⁹ metric tons of dry biomass/year with an energy content of 3.8 × 10⁹ barrels of oil.

Challenge: supramolecular structure of cellulose

The structure of cellulose is complex and interesting. Four different polymorphs are known, cellulose I, II, III, and IV. Cellulose I is the form found in nature and it occurs in two allomorphs, Iα and Iβ. Cellulose II results from re-crystallization or mercerization with aqueous NaOH, and is the most thermodynamically stable crystalline form. In cellulose I the chains run in parallel and in II in antiparallel direction [54]. Celluloses III_I and III_II are obtained by liquid NH₃ treatment of

Opportunities: non-derivatizing solvents for cellulose

The choice of solvent is a compromise between solvent selectivity, capacity, toxicity, physical properties, and solvent recovery capability, but the first criterion to consider in evaluating a solvent system is its capacity to dissolve the material of interest [74]. The most widely used methods for processing cellulose involve chemical reactions to produce cellulose derivatives that are soluble [27]. For example, the Viscose process for producing Rayon fibers is based on the reaction of

Recent developments on cellulose dissolution

It becomes apparent from the above foray into the literature that, even for the better-studied solvents for cellulose, i.e., aqueous NaOH, NMMO·H₂O, and DMAc/LiCl, several issues remain outstanding with respect to fundamentals (solvent-cellulose interactions, solution thermodynamics •155, •156, •157) and to process engineering (dissolution kinetics). In the translation of published research into solvent-based cellulosic pretreatment and dissolution operations for the production of valuable

Conclusions

Given the established applications and great potential of cellulose, the question arises as to why many problems related to cellulose dissolution remain unresolved. The complexity of cellulosics is partly to blame, but there may also be “cultural” issues [54]: “Cellulose research is still largely executed by specialists – ‘cellulose chemists’, ‘textile chemists’ or ‘wood chemists’ – who might occasionally miss a broader picture in scientific development. […] Similarly, cellulose chemistry is

Conflict of interest statement

Nothing declared.

Acknowledgements

We thank the U.S. National Science Foundation (Grant CBET-1159981) for supporting research on cellulose dissolution in our laboratory.

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Review articleSolvent processing of cellulose for effective bioresource utilization

Introduction

Section snippets

Motivation: processing of biomass to valuable products

Challenge: supramolecular structure of cellulose

Opportunities: non-derivatizing solvents for cellulose

Recent developments on cellulose dissolution

Conclusions

Conflict of interest statement

Acknowledgements

Bioresour Technol

Carbohydr Polym

Carbohydr Polym

Carbohydr Polym

Prog Polym Sci

Carbohydr Polym

Prog Polym Sci

Bioresour Technol

Bioresour Technol

Biotechnol Adv

Fuel Process Technol

Bioresour Technol

Biophys J

Carbohydr Polym

Biochim Biophys Acta

Carbohydr Polym

Carbohydr Res

Prog Polym Sci

Prog Polym Sci

Polymer

Polymer

Chemistry and applications of polysaccharide solutions in strong electrolytes/dipolar aprotic solvents: an overview

Molecules

Review of cellulose non-derivatizing solvent interactions with emphasis on activity in inorganic molten salt hydrates

ACS Sustain Chem Eng

The relevance of structural features of cellulose and its interactions to dissolution, regeneration, gelation and plasticization phenomena

Phys Chem Chem Phys

Synthesis of transportation fuels from biomass: chemistry, catalysts, and engineering

Chem Rev

Cellulose: fascinating biopolymer and sustainable raw material

Angew Chem Int Ed

Cellulose-based sustainable polymers: state of the art and future trends

Macromol Rapid Commun

Functionalized polymers from lignocellulosic biomass: state of the art

Polymer

Cellulosic nanomaterials in food and nutraceutical applications: a review

J Agric Food Chem

A review of cellulose and cellulose blends for preparation of bio-derived and conventional membranes, nanostructured thin films, and composites

Polym Rev

Cellulose-based supercapacitors: material and performance considerations

Adv Energy Mater

Wood-derived materials for green electronics, biological devices, and energy applications

Chem Rev

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Rep Prog Phys

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Express Polym Lett

Nanocelluloses as innovative polymers in research and application

Adv Polym Sci

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Chem Rev

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J Mater Sci

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Macromolecules

Rheological properties of oppositely charged polyelectrolyte – surfactant mixtures: effect of polymer molecular weight and surfactant architecture

Macromolecules

Cellulose modification by polymer grafting: a review

Chem Soc Rev

Cellulose solvents – remarkable history, bright future

ACS Symp Ser

Structures of cellulose in solution

Macromol Chem Phys

Dissolution of cellulose with ionic liquids and its application: a mini-review

Green Chem

New water-soluble cellulosic polymers: a review

Macromol Mater Eng

Acylation and carbanilation of cellulose in ionic liquids

Green Chem

Catalytic transformation of lignocellulose into chemicals and fuel products in ionic liquids

Review article
Solvent processing of cellulose for effective bioresource utilization