IRJMST Vol 6 Issue 6 [Year 2015] ISSN 2250 – 1959 (0nline) 2348 – 9367 (Print)

Recent Developments in Green Chemical Extraction Techniques

Manoj K S Chhangani
Government Meera Girls‘ College
Udaipur-(Raj.) India
E-mail: dr.mksc@gmail.com

Abstract:
Society is now more concern about the negative impacts of fossil fuels on the environment. Biomass
is a one of few sustainable alternatives to fossil fuels and a source of renewable carbon, but the bio-
refineries are not in fact green, as sketched by the 12 Principles of Green Chemistry given by Paul
Anastas and John Warner. Many of the bio-refineries involve the extraction of natural polymers and
other valuable materials from lingo-cellulosic biomass in initial processing steps. At this stage,
solvents and reagents used to dissolve and extract cellulose from lingo-cellulosic materials are toxic
and harmful to the environment. An attempt has been made in this paper to focus on recent
developments of alternative green chemical extraction techniques, (1) the use of ionic liquids and (2)
supercritical carbon dioxide. Attempt has also been made to discuss the applicability of these
methods. Current status and challenges are also highlighted.
Keywords:
Introduction

Fossil-based energy resources are accountable for three-fourth of the world‘s primary energy
consumption. Crude oil has become eminent feedstock in the manufacture of many consumer
products such as plastics, fertilizers, clothing, cosmetics and building materials.1-5 Fossil independent
era will be achieved in two pace, firstly improvement in the present fossil fuel-based systems6 and
secondly the advancement of existing technologies to take total advantage of renewable energy
resources.5 At this time bio-refinery (i.e. refinery of biomass) concept have been introduced as
progeny to fossil fuels and oil-based refineries.5,7-9 Biomass is existing in abundant amount and a
renewable as well as sustainable source of carbon.7 Carbon dioxide generated in the energy
conversion of bio-fuels is seized back into biomass in the biogeochemical cycling of carbon and
make the process to carbon-neutral.4 It is important to understand here that bio-refineries are not
inherently green. Intrinsically green bio-refineries are only possible when principles of green
chemistry essentially incorporated in the development of next-generation bio-refineries, which will
be a truly sustainable alternative to conventional fossil-based system. These principles include:
utmost conversion of the feedstock into the final product (atom economy), reduced energy
consumption, use of safer materials and processes, generation of non-toxic and totally biodegradable
products.7 Thus, the idea of development of green and sustainable bio-refineries is much beyond
simply the use of renewable feedstock.

Figure 1 represents a sketch of some significant extractives, and their downstream chemicals, that
can be achieved from biomass.7 The operation of the perfect bio-refinery can be segregated into two
sections: 8

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IRJMST Vol 6 Issue 6 [Year 2015] ISSN 2250 – 1959 (0nline) 2348 – 9367 (Print)

1. Production of high-value low-volume (HVLV) extractives; and

2. Conversion of low-value high-volume (LVHV) intermediates into energy and fuel products.
As shown by figure 1, the extraction of natural polymers from biomass constitutes the initial
processing steps of many bio-refineries.7-10 Thus, the development of competent and environment
friendly extraction techniques will be a field of research with important implications to the expansion
of green bio-refineries.

Figure 1 Simplified bio-refinery flowchart

The biomass which will be utilized by future supply chains having enormous variety. The vast array
of different biomass is a major challenge to the development of extraction techniques for next-
generation bio-refineries. These feedstock comprise of low-value plants (trees, grasses and heathers),
byproducts from energy and food crops, marine resource and food wastes.9

This paper concentrates on the recent development of solvent-based green extraction techniques (1)
the use of ionic liquids11,12 and (2) supercritical carbon dioxide (scCO2)13,14 for the treatment of
plant-based lingo-cellulosic feedstock.

Ionic Liquids

A group of organic salts that exist in the liquid state at moderately low temperatures (< 100 °C)
termed as ‗ionic liquids‘ (ILs).15, 16 The use of ionic liquids such as volatile organic compounds
(VOCs) as alternatives to conventional industrial solvents and environment friendly solvent attain
significant interest in last decade.17 Advantages to ionic liquids in the perspective of green chemistry
are-

1. ionic liquids are non-volatile (therefore no pollution of VOCs into the atmosphere17,18,
2. they have high solubility for a wide range of inorganic as well as of organic materials, thus
requiring less volumes of solvent18, and
3. they can be designed to be environment friendly.17

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Also, through the utilization and design of ionic liquid solvents optimization of reactions (yield and
selectivity) can be achieved. 18

Rogers et al. extensively worked on development of ionic liquids to dissolve cellulose. 16 Solubility
up to 25 wt % was achieved by them using ionic liquids, containing 1-butyl-3-methylimidazolium
cations and chloride anions, along with microwave heating.16 The solubility of cellulose depends on
the potential of the solvent molecules to tangle and penetrate the strong, intra-molecular hydrogen-
bond network of supra-molecular cellulose structures.19 The solubility capacity of these solvents is
directly related to the mobilization and interaction of the chloride ions with the cellulose hydroxyl
groups.16,20 Small anions (hydrogen bond acceptors) such as chlorides have been shown to be most
effective for cellulose dissolution.16,20 Ionic liquids with cations based on cores of
methylimidazolium (MIM) and methylpyridinium (MPy) have been found to produce immense
results.20 Thus, ionic liquids offer an inherent advantage over conventional solvent systems.

At the same time, a compromise between rheological properties and solubility ability of ionic liquids
is a main inadequacy designing ionic liquids for industrial applications.16 In addition, the solubility of
cellulose in ionic liquids was found to be highly sensitive to water impurities.16 Review of literature
also reveals that there have also been some discrepancies in the literature as to whether ionic liquids
are in fact ‗green‘, due to the toxicological properties and environmental impacts associated with
some ionic liquid solvents. 21-23

Supercritical CO2

Natural waxes consist of complex mixtures of large chain fatty acids and alcohols, sterols and
alkanes.24 In conventional extraction of these waxes harsh volatile organic solvents such as hexane,
chloroform, and benzene are involved.25 Processes involving these solvents are highly unselective
because not only of co-extraction of many unwanted compounds, but also for environmental and
toxicological concerns associated with these solvents. 25 Thus, an alternate non-toxic, environment
friendly and selective extraction methods for waxes from bulk lignocellulosic materials is
necessitating.25

The application of supercritical fluids (SCF) such as supercritical CO2 (scCO2), for the extraction
and fractionation of waxes has been come across considerably in the literature.9-10,25 Liquids and
gases at temperatures and pressures higher than their critical temperatures and pressures are termed
as supercritical fluids.26 At the temperatures and pressures above the critical point the liquid-vapor
phase boundary vanishes and the phase at this stage exhibits properties between those of gas and
liquid. High compressibility of supercritical fluids in the zone of the critical point makes it simple to
adjust density and solution ability by a small change of temperature or pressure. This property
provides ability to the supercritical fluids to dissolve compounds of different polarity and molecular
mass. Carbon dioxide (scCO2) is one of the widely used supercritical fluids, achieving the green
chemistry goals.

SCF systems for extraction generally make use of scCO2 because of comparatively low critical
temperature (31.1 °C) and pressure (73.8 bar), low cost and non-toxicity of scCO2.26 Extremely
tunable property of scCO2 by adjusting the extraction parameters (i.e. temperature, pressure, flow

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rate, etc.) make it more advantageous than other conventional solvents.9,25 Wonderful control over
the selectivity of wax products which are dissolved25 allows for rational fractionation of the various
wax components is another advantage of scCO2 extraction methods.25 Unchanged structure of the
bulk material after extraction allows for easy integration into next-generation bio-refineries.9,25 The
extraction and fractionation of wax products from wheat straw using scCO2 yielded an optimum
extraction time for the recovery of 99.9% of total extractable wax products. 25 This method reported
by Clark et al. is currently patented and shows absolute assurance for incorporation in bio-refineries.

Though, there are some challenges to SCF extractions that still remain, a great extent of progress has
been made in terms of the improvement of best possible extraction parameters (i.e. temperature,
pressure, etc.),25-28 however there is still space for advancement, including the fractionation of other
secondary metabolites from a wider range of materials. In addition, the cost factor associated with
SCF extraction methods is also a noteworthy barrier in some industrial applications.26

Conclusion

The advancement of green and sustainable bio-refineries is a great demand of present era. The focal
point of this paper is the importance of green chemical extraction techniques, which forms the initial
processing steps of many next-generation bio-refineries. These methods will need to be adaptable to
a wider range of materials and produce good separation of natural polymers and secondary
metabolites for further modification into fuel and valuable consumer products. Recent development
to ionic liquids16 and scCO225 have been assuring for significant tunability for application in diverse
materials with ever improving yields. However, for integration into future bio-refineries, there is still
much space for upgrading. For ionic liquids, these include: improvements to the rheological
properties of ILs without compromise to its solubilizing power16, robustness of ILs in the presence of
water impurities16 and further improvements to yield and energy-efficiency.24 For scCO2, the high
costs associated with its implementation to industrial scales will be its biggest obstacle.26

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