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This paper reviews the application of ionic liquids to the deconstruction and fractionation of lignocellulosic biomass, in a process step that is commonly called pretreatment. It is divided into four parts: the first gives background information on lignocellulosic biomass and ionic liquids; the second focuses on the solubility of lignocellulosic biomass (and the individual biopolymers within it) in ionic liquids; the third emphasises the deconstruction effects brought about by the use of ionic liquids as a solvent; the fourth part deals with practical considerations regarding the design of ionic liquid based deconstruction processes.

Fossil fuel resources are not limitless so alternative renewable recourses are needed to fill the void that inevitably will be created once the supplies of this resource start do dwindle. Biomass has the potential to fill this void. Today only a small part of the world annual production of biomass is utilized by humankind, while the rest is allowed to decay naturally. To utilize this renewable resource in the production of fuel and chemicals, the so called bio-refineries specialized in fractionation and making use of all component of the biomass are needed. Ionic liquids could aid in this task.

Ionic liquids (ILs) have shown great potential in the field of biomass processing in general and in the pretreatment of (ligno)-cellulose in particular. However, a few things need to be addressed before any large-scale processing can be considered: Finding new routes for IL synthesis that make "on-site" production possible; Investigation into the challenges facing IL pretreatment of (ligno)-cellulose such as possible depolymerization of cellulosic material during the pretreatment and investigating what influence different ILs have on the pretreatment of cellulosic material by methods like enzymatic hydrolysis.

This work aims to address these issues and will present a route for IL synthesis making use of alcohols and carboxylic acids both commonly found in a biorefinery. Some of these ILs have also been tested for their ability of dissolve cellulose. Furthermore, this work will address the possibilities but also challenges upon IL-mediated (ligno)-cellulose processing. This includes investigating several ILs and their efficiency as a pretreatment solvent for enzymatic hydrolysis; these studies involve a large variety of different cellulosic materials. This work demonstrated that depolymerization during the IL pretreatment is a possibility and that this can complicate the recovery processes. Furthermore, this work gives guidance into what type of ILs might be suited as pretreatment solvents for different cellulosic materials, including amorphous and crystalline cellulose, processed and native lignocellulose, different types of wood samples and hemicellulose.

This work demonstrates a novel synthesis route to halogen-free ionic liquids. A one-pot synthetic reaction route avoiding the use of toxic and high-energetic alkyl halides was developed to reduce the environmental impact of the synthesis process of ionic liquids. However, the elimination of halogens and alkyl halides in the preparation of ionic liquids is not just an environmental issue: the aforementioned species are also among the most common and persistent contaminants in today’s Ionic Liquids (ILs). Thus, this paper introduces a range of quaternized nitrogen based ionic liquids, including both aromatic and non-aromatic components, all prepared without alkyl halides in any step of the process. Moreover, bio-renewable precursors such as (bio-)alcohols and carboxylic acids were employed as anion sources and alkylation media, thus avoiding halogen contamination or halogen-containing anions. The IL’s prepared were designed to dissolve cellulose, some of which was included in a cellulose dissolution study using a sulphite cellulose from the company Domsjö.

It is commonly accepted that world-wide production of oil, coal and natural gas will eventually come to a halt, although we still heavily depend on these non-renewable feed stocks and their associated chemical derivatives. Therefore, new, sustainable resources for the production of industrially important chemicals are required. Biomaterials offer much promise in this regard, since they generally contain a lot of cellulose which can be transformed and potentially provide a great source of industrially important chemicals. Presently, only a small part of the annual biomass growth in the world is utilized by industry, while the rest is decaying along natural pathways. In order to effectively process cellulose, it needs to be dissolved in some liquid medium. Present state-of-the-art commercial technologies employ very toxic and hazardous processing with volatile organic solvents like CS2. However, this need not be the case. Ionic liquids (ILs) have shown great potential for the dissolution of cellulose. Some ILs also have attractive physical properties such as: low vapor pressure, high thermal stability and reusability. Thus, they are potentially viable and more environmentally friendly alternatives. Hereby, we present and discuss some of the challenges and perspectives for ILs in terms of their potential for cellulose processing. We briefly review the historical processes and current methods for cellulose processing, and look at alternative processes taking advantage of ILs.

The goal of the present study, devoted to wood fractionation, was to obtain monosaccharides, hexoses and pentoses by means of an ionic liquid (IL) based pre-treatment procedure. Softwood sawdust (maximum particle size of 2 mm) of Scots pine (Pinus sylvestris) and Norway spruce (Picea abies) were exposed to ionic liquids – 1-ethyl-3-methylimidazolium acetate (C2mimAce) and 1-ethyl-3-methylimidazolium chloride (C2mimCl) – and thermal treatment (80-150 °C), for various time intervals (0-72 h). Furthermore, cellulose of various origins (plants, wood pulps) was dissolved in C2mimAce and 1-butyl-3-methylimidazolium chloride (C4 mimCl) for the study of the dissolved fractions, stress being laid on monosaccharides and possible by-products, 5-hydroxymethylfurfural and furfural. Knowing the challenges in analysis techniques when ILs and sugars are involved, the present work focuses on the development of suitable analysis methods. To this end, a Hewlett Packard 1100 series HPLC equipped with a refractive index (RI), detector model HP1047 A and a diode array UV detector (DAD) fitted with a carbohydrate column HPX-87K was utilized. Challenges and improvements are discussed.

BACKGROUND Enzymatic hydrolysis of cellulose in lignocellulosic materials suffers from slow reaction rates due to limited access to enzyme adsorption sites and to the high crystallinity of the cellulose. In this study, an attempt was made to facilitate enzymatic hydrolysis by pretreatment of cellulosic materials using the ionic liquid (IL) 1-allyl-3-methylimidazolium formate ([Amim][HCO2]) under mild reaction conditions. The effect of the IL was compared with that of thermochemical pretreatment under acidic conditions.

RESULTS The lignocellulosic substrates investigated were native and thermochemically pretreated Norway spruce and sugarcane bagasse. Microcrystalline cellulose (Avicel) was included for comparison. The IL treatments were performed in the temperature range 45–120 °C and, after regeneration and washing of the cellulosic substrates, enzymatic saccharification was carried out at 45 °C for 72 h. After 12 h of hydrolysis, the glucose yields from regenerated native spruce and sugarcane bagasse were up to nine times higher than for the corresponding untreated substrates. The results also show positive effects of pretreatment using [Amim][HCO2] on the hydrolysis of xylan and mannan.

Conclusion The present work demonstrates that both native wood and agricultural residues are readily soluble in [Amim][HCO2] under gentle conditions, and that pretreatment with ionic liquids such as [Amim][HCO2] warrants further attention as a potential alternative to conventional pretreatment techniques. © 2013 Society of Chemical Industry

Background: Ionic liquids (ILs) draw attention as green solvents for pretreatment of lignocellulose before enzymatic saccharification. Imidazolium-based ILs with different anionic constituents ([HSO₄]⁻, [Cl]⁻, [MeCO₂]⁻) were compared with regard to pretreatment of wood from aspen and spruce. The objective was to elucidate how the choice of anionic constituent affected the suitability of using the IL for pretreatment of hardwood, such as aspen, and softwood, such as spruce. The investigation covered a thorough analysis of the mass balance of the IL pretreatments, the effects of pretreatment on the cell wall structure as assessed by fluorescence microscopy, and the effects of pretreatment on the susceptibility to enzymatic saccharification. Torrefied aspen and spruce were included in the comparison for assessing how shifting contents of hemicelluloses and Klason lignin affected the susceptibility of the wood to IL pretreatment and enzymatic saccharification.

Results: The glucose yield after IL pretreatment increased in the order [Cl]⁻ < [HSO₄]⁻ < [MeCO₂]⁻ for aspen, but in the order [HSO₄]⁻ < [Cl]⁻ < [MeCO₂]⁻ for spruce. For both aspen and spruce, removal of hemicelluloses and lignin increased in the order [Cl]⁻ < [MeCO₂]⁻ < [HSO₄]⁻. Fluorescence microscopy indicated increasingly disordered cell wall structure following the order [HSO₄]⁻ < [Cl]⁻ < [MeCO₂]⁻. Torrefaction of aspen converted xylan to pseudo-lignin and changed the glucose yield order to [HSO₄]⁻ < [Cl]⁻ < [MeCO₂]⁻.

Conclusions: The acidity of [HSO₄]⁻ caused extensive hydrolysis of xylan, which facilitated pretreatment of xylan-rich hardwood. Apart from that, the degree of removal of hemicelluloses and lignin did not correspond well with the improvement of the enzymatic saccharification. Taken together, the saccharification results were found to mainly reflect (i) the different capacities of the ILs to disorder the cell wall structure, (ii) the recalcitrance caused by high xylan content, and (iii) the capacity of the [HSO₄]⁻-based IL to hydrolyze xylan.