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DEEP EUTECTICS SOLVENTS - NEW TYPE OF

TECHNOLOGY FOR BIOREFINERY

Conference Paper · March 2015

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Michal Jablonsky Ales Haz

Slovak University of Technology in Bratislava Slovak University of Technology in Bratislava
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Slovak University of Technology in Bratislava Slovak University of Technology in Bratislava
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 DEEP EUTECTIC SOLVENTS - NEW TYPE OF TECHNOLOGY
FOR BIOREFINERY
Andrea Škulcová, Michal Jablonský, Aleš Ház, Alexandra Sládková, Lenka Dubinyová, Igor Šurina
Slovak University of Technology, Faculty of Chemical and Food Technology, Institute of Natural and Synthetic Polymers, Department of Wood, Pulp and Paper,
Radlinského 9, 812 37 Bratislava
xskulcova@stuba.sk

Abstract

Biomass plays an important role in future energy infrastructure to produce electricity and heat, but also for the production of materials, chemicals and
fuels. Fractionation on raw materials is an essential operation for almost all processes acquiring other products. A simple and clean fractionation of the
main components of biomass represents a very important step in the "clean", renewable carbon economy. If we can easily separate the different
components, we gain a significant source of raw material. These can be further used as a starting material for new composites, fibres, biopolymers, but
also value-added chemicals as well as fuels. The important group of new advanced solvents that can be used to dissolve lignocellulosic biomass and its
processing is the next generation of ionic liquids known as deep eutectic solvents (DES). The deep eutectic solvents are breakthrough discovery and open
the way to the pulp production at low temperatures and at atmospheric pressure. The advantage of using the proposed selective fractionation process is
the possibility of separating the various components of lignocellulosic matrix: first extractives, followed by extraction of lignin and polysaccharides. Deep
eutectic mixtures have a great potential as the new green technology in biorefinery concept.

Introduction

Due to the reduction of fossil resources is constantly coming in newer and more efficient ways to use biomass. The biorefinery concept has a task of the
implementation of new conversion processes and equipments to fuels, energy and chemical production. However, the obstacles are still technological
limitations and economic feasibility [1]. For this very reason it is necessary to interested in development of technological processes of treatment
lignocellulosic materials.
Cellulose and lignin are among the two most widespread natural organic polymers on the Earth. They formed the base of plants together with
hemicelluloses. In the context of biorefinery can be lignocellulose seen as a sustainable and renewable source of fuels and chemicals. In this case is
necessary to separate lignin from holocellulose and it is “critical step”. Relatively new and economically interesting way of separating is using DES (Deep
Eutectic Solvents). [2]

Deep eutectic solvents

DES are two or more component mixture formed between a variety of green solvents natural origin
organic acids, amino acids, alcohols, choline derivatives, sugars or non – flammable biodegradable
inorganic compounds and salts. They are mostly liquids at room low volatility safe
temperature (23±1 °C) with melting points much lower than melting points environmentally benign cheap
of the compounds that form this mixture (Figure 1). Some DES are at room
temperature still almost solid with visible crystals that are one of the
compounds. If the mixture would be heated, crystals dissolved (Figure 2, 3).
They also share a lot of characteristics with ionic liquids (ILs) but ILs
are solvents composed entirely of paired ions and DES have
hydrogen bonding. ILs are synthesized from petrochemical resources
while deep eutectic solvents are mostly synthesized from natural
materials (from plants, insects, animals or micro-organisms). DES
have been known for years but they received our attention in 2003
when Abbott et al. [3] used choline chloride and urea mixture as
a solvent and in 2004 when Abbott et al. [4] published work that
connects ionic liquid and deep eutectic solvents and call them
Figure 2: Lactic acid:choline lactate „suitable solvents“.
(2:1) [2]

Figure 1: The temperature dependence of the

Figure 3: Glycolic acid:choline chloride
composition of the eutectic mixtures (Abbott) (3:1)
References
[1] A.M. da Costa Lopes, K.G. Joao, D.F. Rubik, E. Bogel-Lukasik, L.C. Duarte, J. Andreaus,
R. Bogel-Lukasik. Pre-treatment of lignocellulosic biomass using ionic liquids: White straw
fractionation. Bioresource Technology 2013, 142, 198-208.
[2] S.L.G. de Dios. Dissertation thesis. University of santiago de compostela school of
engineering, Department of Chemical Engineering. Phase equilibria for extraction processes
with designer solvents. Santiago de Compostela, September 2013.
[3] A.P. Abbott, G.Capper, D.L. Davies, R. K. Rasheed, V. Tambyrajah. Novel solvent
properties of choline chloride/urea mixtures. Chemical Communications 2003, 70–71.
[4] A.P. Abbott, D. Boothby, G. Capper, D. L. Davies, R. K. Rasheed. Deep eutectic solvents
formed between choline chloride and carboxylic acids: versatile alternatives to ionic liquids.
Journal of the American Chemical Society 2004, 126, 9142-9147.
[5] M.C. Francisco, A. van den Bruinhorst, M.C. Kroon. Low-Transition-Temperature Mixtures
(LTTMs): a new generation of designer solvents. Angewandte Chemie 2013, 52(11), 3074-
3085.
Fractionation of biomass
The base of paper production is treatment of biomass. The most
important step is fractionation of biomass to polysaccharides and
lignin. In present, for removal of lignin is primary used delignification
by Kraft process. The significant disadvantages are high water
consumption and formation of sulphur compounds. There are some
papers in which was researched isolation of lignin from wood or straw
[2, 5]. DES is continuously stirring, at least 16 hours, with wood or
straw sawdust at temperature 60 – 90 °C (depending on DES
Figure 4: Lactic viscosity). After centrifugation is precipitate filtered and dried
acid:choline chloride and
pine wood [2] (Figure 4).
There is possibility to find effective mixtures to selective fractionation
of lignin. It can be the first step to new green way of delignification
with using DES.

This work was supported by the Slovak Research and Development Agency under the contract No. APVV-0850-11
and by National centre for research and applications of renewable sources of energy ITMS 26240120016.

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