Journal of Polymers and the Environment

https://doi.org/10.1007/s10924-023-02817-x

REVIEW

A Review on Eco‑friendly Isolation of Lignin by Natural Deep Eutectic

Solvents from Agricultural Wastes
Aatikah Meraj1 · Surendra Pratap Singh2 · M. Jawaid3 · Mohamed Mahmoud Nasef4,5 · Taghrid S. Alomar6 ·
Najla AlMasoud6

Accepted: 20 February 2023

© The Author(s), under exclusive licence to Springer Science+Business Media, LLC, part of Springer Nature 2023

Abstract
Agricultural residues have attracted the attention of researchers in recent years due to their potential as a waste source
that is abundantly available worldwide and can be used to create value-added products with economic and environmental
benefits. Lignin is the second most inexhaustible natural biopolymer, delivering the most energetic material of all for the
development of eco-friendly, biodegradable, and low-cost value-added products. Commonly lignin used as a macromolecule
for the synthesis of low molecular weight chemical sand fuel. The present review article tries to present to fulfil research
gap between extraction and isolation of lignin through natural deep eutectic solvents (NADES), green/sustainable methods
which is fast-emerging techniques to extract valuable products. In this review article, we covered various methods on pre-
treatment of lignocellulosic materials using NADES as exclusive and multifunctional solvents via the green integrated
biorefinery approach. It also contains comparison between advantages and disadvantages of pre-treatment methods vs
NADES of various biomass. Beside those various methods of sustainable synthesis of NADES and its properties; processing
of lignin for production of value–added products, applications of lignin derived by green synthesis, and challenges to current
state-of-the art technologies and future perspectives and current Markets are reviewed. We concluded that NADES can be
effectively used for low-cost synthesis in the purification and isolation of lignin from agro wastes for attaining high yields
which ultimately enhance economic value of lignocellulosic biomass.

Keywords Lignocellulosic biomass · Pre-treatment · Biorefinery · Lignin · Natural deep eutectic solvents

* M. Jawaid Introduction
[email protected]
1
Laboratory of Bio‑polymer and its Derivatives, Institute Plant biomass (lignocellulosic), the world's most abundant
of Tropical Forestry and Forest Products (INTROP), renewable resource and primary source of lignin, has been
Universiti Putra Malaysia, UPM, 43400 Serdang, Selangor, identified as a potential source of chemicals and biomateri-
Malaysia
als. Thus, in today's industrial world, lignocellulosic plant
2
Pulp and Paper Research Institute, materials are the most promising feedstock as a renewable
765017 Jaykaypur, Rayagada, Odisha, India
and natural resource [1]. Natural sources of lignocelluloses
3
Laboratory of Biocomposite Technology, Institute of Tropical include grass, agricultural residues, wood, municipal solid
Forestry and Forest Products (INTROP), Universiti Putra
Malaysia, UPM, 43400 Serdang, Selangor, Malaysia wastes and forestry wastes, [2]. This has made lignocel-
4 lulose, which is produced by photosynthesis, abundant,
Department of Chemical and Environmental Engineering,
Malaysia-Japan International Institute of Technology, cheap and widely utilized in various renewable energy
Universiti Teknologi Malaysia, Jalan Sultan Yahya Petra, and environmental applications [2, 3]. Lignocellulosic
54100 Kuala Lumpur, Malaysia biomass species are composed of cellulose, holocellulose,
5
Center of Hydrogen Energy, Institute of Future Energy, hemi-cellulose, lignin, volatile and non-volatiles extrac-
Universiti Teknologi, Jalan Sultan Yahya Petra, tives, lignols, and various inorganic elements in a highly
54100 Kuala Lumpur, Malaysia complex architecture; the structural and compositional
6
Department of Chemistry, College of Science, Princess properties of lignocellulosic biomass create formidable
Nourah Bint Abdulrahman University, Riyadh 11671, barriers to its destruction occurring during biotechnical/
Saudi Arabia

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 Journal of Polymers and the Environment

Fig. 1  A 3D view of the lignin–

carbohydrate complex in the
wood cell wall [5]

chemical biorefinery pre-treatment operations [4]. Fig- and because of the possible negative environmental impact,
ure 1 describes the typical structure of lignin–carbohydrate the final disposal off agricultural food waste has become a
complex (LCC) chemically bonded rather in a complex serious concern for food processing enterprises [12].
form instead of not just being attached in a simpler form Lignin has a complex and irregular structure contain-
which make LCC structurally rigid complex. Therefore, ing various organic and inorganic impurities and having a
this complex exhibits the original structure of lignocel- unique chemical reactivity, its shown in Fig. 2. Particularly
lulosic biomass inheriting different composition and fea- lignin has a three-dimension highly cross-linked biopoly-
tures. Thus, Fig. 1 showing 3D structure in wood cell wall mer constructed from three substituted phenols including
exhibiting ether linkage between carbohydrate and lignin coniferyl, sinapyl, and p-coumaryl alcohols [3]. These fea-
giving plant cell wall strength and structure [5, 6]. tures depend on the source of plant biomass species and the
Lignin is a vital carbohydrate polymer found in the methods of isolation and affect not only the lignin physical,
cell walls of many different types of biomass cells such chemical, and thermal properties but also its utilization [13].
as wood and bark. It is a biopolymer with a high degree This has made lignin extraction a complex process and led to
of heterogeneity. Generally, on a dry weight basis, extensive research work on the development of lignin isola-
lignocellulosic biomass contains 44% to 52% cellulose, 28% tion and pre-treatment methods involving diverse biological,
to 31% hemicellulose, and 16–25% lignin [7]. Lignin is well- physical, physic-chemical, and chemical approaches that are
known as the second most inexhaustible natural biopolymer, customized to suit lignin raw biomass source and desired
delivering the most energetic material of all, allowing plants application. Even though lignin is a desirable and renewable
to create stable chemical structures, and offering a resistance resource, lignin valorisation is mainly limited by two major
to solubility, thereby inhibiting hydrolysis of cellulose and issues: (a) Inefficient lignocellulosic biomass separation
hemicellulose in lignocellulosic biomass. This possesses into various streams i.e.; lignin-rich and carbohydrate-rich
an important challenge for the isolation of the respective streams, (b) undesirable lignin condensation at the expense
biopolymers in the biomass. Lignin accounts for 16–30 of cleavable inter-unit ether linkages (β-O-4 linkages) upon
wt% of lignocellulosic biomass and is a critical constituent biomass pretreatment [14–16]. Overall, lignin valorisation
in current and future biorefineries, making its valorisation can help minimise waste, generate new revenue sources, and
critical [8]. Lignin is also available in black liquor. Black promote sustainability (Fig. 2).
liquor is promising by-product of pulp industry, mostly Lignin is conventionally extracted in the industry using
used as a fuel to recover energy. However, because of the Soda, Kraft, and Sulfite processes in which the lignin
huge quantities produced, lignin is rapidly being explored undergoes severe hydrolytic degradation reducing the
as a potential chemical source, and studies of its thermal quality of lignin and its suitability for many value-added
destruction are receiving a lot of attention [9]. Globally, it applications. Moreover, these methods are cost-intensive
is estimated that agricultural food waste amounts to 5 billion and leave chemical waste, and pose serious environmental
tons of lignocellulosic biomass residues per annum. The challenges in addition to compromising the purity [13,
total annual bio-waste generated in the European Union is 17]. Green extraction methods of lignin using combined
estimated to be between 76.5 and 102 million tonnes [10, 11] organosolv and enzymatic hydrolysis, water subcritical and

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Fig. 2  Lignin extraction and transformation from different NADES system [134] (With Permission)

supercritical, deep eutectic solvents, ionic liquid co-solvents materials [24], comparative analysis of various pre-treat-
provide alternative environmentally friendly, value adding ment strategies [25], the problems hampering the utiliza-
and sustainability [18–23]. An immense research work tion of technical lignin’s and ways to overcome have been
has been carried out to extract lignin for wood and non- published [17]. However, a review of the progress in the
wood (sugarcane bagasse, bamboo, wheat straw, corn green (sustainable) lignin isolation methods can be barely
stover, alfalfa, kenaf and flax fibres) biomass sources [3] found. Therefore, we have discussed the green method of
and the progress in this field have been reviewed in various lignin extraction by using the NADES method. The market
occasions [20, 24]. for NADES is still in its early stages, but it is expanding
There have been many review articles on extraction as additional applications for these solvents are discovered
and isolation of lignin with the focus given to isolation and their potential as a sustainable alternative is better
methods on raw biomass. For example, fundamental of acknowledged. In recent years, there has been a grow-
lignin chemistry and the potential application in develop- ing interest in creating and implementing greener, more
ing biomaterials [13], the relation between lignin extrac- sustainable technologies, which is increasing demand for
tion processes and the resource supply, and in bio-based NADES. However, with an emerging market there are

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challenges that need to overcome, such as a lack of stand- from straw, stem and leaves etc. [28]. Wastes generated are
ardisation and the need for additional research and devel- abundant and rich in composition which can be used and
opment to fully fulfil potential of these solvents. reused in economic and environmental point of view to value
In this review article, we have discussed various methods added products.
for the pre-treatment of lignocellulosic materials using The most common agricultural crops with the highest
Natural deep eutectic solvents (NADES) as exclusive and production and area under cultivation are maize, wheat,
multifunctional solvents via the green integrated biorefinery rice, and sugarcane. These four crops provide the vast bulk
approach. It also done a comparison between the advantages of lignocellulosic biomass in the agricultural sector, with
and disadvantages of pre-treatment methods vs NADES the remaining waste accounting for only a small percentage
of various biomass. Beside those Various methods of of global agricultural waste output [29]. Additionally,
sustainable synthesis of NADES and its properties; the because of their year-round availability, the four major crops
processing of lignin for the production of value–added described above are the most advantageous feedstocks for
products, Applications of lignin-derived by green synthesis, bioethanol or liquid fuels production [30].
and Challenges to current state-of-the-art technologies and
future perspectives and Current Market.
Various Partial Lignin Removal Methods

Agricultural Waste Available for Lignin The surface and internal structure of lignocellulose, as
Extraction well as its chemical composition, must be modified during
the pre-treatment to enable faster and more effective
Agricultural waste is a significant source of biomass energy hydrolysis of the carbohydrate part into monomeric sugars
and biobased products. The utilization of agro-industrial [31, 32]. Hence, the ultimate purposes of pre-treatment are
residues as raw materials can lower production costs while summarized as follow [31, 33–36]:
simultaneously lowering pollutant in the environment. In
nations like India, where benign, viable energy resources • Prevent the synthesis of inhibitory by-products via
are highly needed, proper use of agricultural waste could hydrolysis and fermentation by splitting the complex
lead to long-term rural development [26]. Lignocellulosic network of lignin-hemicellulose-cellulose to obtain
biomass can be obtained from forest debris, agricultural monomeric unit by chemical or enzymatic treatment
waste products. Biomass resources which are present in • Obtain Lignin by breaking the link between cellulose
fruits, vegetables, agro wastes as well as wastes of municipal and hemicellulose; to prevent the degraded carbohydrate
and industries are categorized based on their physiochemical attainment
character [27]. • Minimize the unusable lignocellulose when obtaining the
Table 1 depicts the composition of lignocellulosic mate- lignin from the plant cell wall
rial is greatly dependent on its raw source, produced during
processing of industrial and agricultural products obtained

Table 1  Chemical composition Types of biomass Lignocellulosic substrates Cellulose (%) Hemicellulose (%) Lignin (%)
of various lignocellulosic
biomass [28] Agricultural wastes Rice straw 32.1 24 18
Corncobs 45 35 15
Wheat straw 30 50 15
Barley straw 33–40 20–35 8–17
Corn stover 39–42 22–28 18–22
Nut shells 25–30 25–30 30–40
Swine waste 6 28 –
Industrial wastes Waste newsprint paper 60–70 10–20 5–10
Organic compound from 8–15 0 0
wastewater solid
Energy crops Switch grass 45 31.4 12
Empty fruit bunch 41 24 21.2
Forestry wastes Leaves 15–20 80–85 –
Softwood stems 45–50 25–30 25–35
Hardwood stems 40–55 24–40 18–25

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• Minimize the size of the particle or enhance the porosity Pre‑treatment Methods
for better engagement of hydrolysing agents for substrate
increased reactivity Mechanical Pre‑treatment

Extreme pre-treatment conditions such as long residence Mechanical pre-treatments of lignocellulosic material
time at high temperatures and acid concentrations can are green significant processes that are needed not only
reduce monomeric sugars content, organic acids, and furan to improve the particle densification by reducing its size
derivatives as well as, to a lesser extent, from phenolic and distribution but also to generate new surface area and
compounds (e.g., lignin) which degrade into aldehydes and improve flow properties as well as increase porosity. By
organic acids. Many of these degradation products have mechanical pre-treatments, such as grinding, and milling
been found to be highly inhibitory to fermentation and thus results in a decrease in particle size and crystallinity.
it is important to optimize the pre-treatment conditions to According to Palmowski et al., a reduction in particle size
minimize the degradation [32, 37, 38], which are mostly not only increases the surface area but also reduced the
produced during pre-treatment with lignocellulosic materials degree of polymerization [53]. A decrease in degrees of
[39]. The type and amount of toxic materials produced are polymerization, depending on the kind of biomass, might
determined by the source materials and the severity of the boost enzymatic hydrolysis by 5–25% [54].
pre-treatment process conditions [40]. Furthermore, various For various pre-treatment methods, mechanical pre-
additional parameters, such as biomass porosity, cellulose treatment is the first stage in the pre-treatment process
fibre crystallinity, hemicellulose and lignin content, have that is followed by a biological treatment. Motte et al.
been reported to influence cellulose hydrolysis. Due to the demonstrated that the dry dark fermentation of wheat
presence of lignin and hemicellulose, cellulase enzymes have straw, which followed the mechanical treatment i.e.,
a great difficulty in accessing the cellulose fibres, lowering centrifugal milling and ball milling at room temperature
the effectiveness of the hydrolysis process [35]. It has been for 5 min, enhanced ethanol output by 83% and boosts
determined that, because different lignocellulosic biomass overall substrate conversion [55]. However, operating
have varying physic-chemical properties, appropriate pre- costs and equipment depreciation are important factors
treatment technologies based on the constituents of the in mechanical pre-treatment. Table 2 shows the usage
biomass must be used [41, 42]. of mechanical pre-treatment in aiding subsequent
Pre-treatments that are capable of sufficiently removing pre-treatments.
lignin are more effective [43–48]. Mechanical pre-treatments
such as ball milling, can improve the digestibility of lingo-
cellulose by reducing lingo-cellulose size and crystallinity Chemical Pre‑treatment
of the lingo-cellulose prior to chemical pre-treatment [49].
The inhibitory compounds generated after pre-treatment are Chemical pre-treatment is a method that uses diverse
classified as: carboxylic acids, furans, phenols, and inorganic chemicals such as acids, alkalis, and organises to pre-
salts. These products are formed because of biomass type treat biomass under different reaction circumstances. Its
and the pre-treatment parameters such as pH, temperature, mechanism varies depending on the chemicals utilized
time, and catalyst addition. During acid pre-treatment, and the conditions of pre-treatment. Apart from the slight
sugar breakdown products such as furfural are produced at limitations in specific chemical pre-treatments, it is a
high concentrations [50] and high temperatures, whereas highly effective technique for the pre-treatment approach
phenols are produced at low concentrations during steam for changing the structure of lingo-cellulose.
pre-treatment [51]. Ion exchange, active coal treatment,
laccase and peroxide pre-treatment, and/or over-liming
can all be used to remove inhibitors, with the last being Acid Pre‑treatment
notably efficient for the removal of furan and phenol [52].
More details on various methods on pre-treatment of Diluted sulphuric acid [59, 60] has been used widely for
lignocellulosic materials are discussed in next section. acid pre-treatment of lignocellulosic biomass while other
diluted acid such as hydrochloric acid [61–63], nitric acid
[64, 65] and phosphoric acid [66–68] have also been inves-
tigated which is summarised in Table 3. In general, acid
pre-treatment dissolves polysaccharide glycosidic link-
ages, releasing individual monosaccharides. However,
even in diluted form, the usage of strong acids such as

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Table 2  Usage of mechanical pre-treatment in other pre-treatments

Biomass Mechanical pretreatment Subsequent pretreatment Reaction conditions Results References

Biologically Treated Centrifugal milling and – Time: 5 min Ethanol yield: 83% [55]
wheat straw ball milling Temp: Room
temperature
Wheat straw Drying and milled in Alkaline peroxide Temp: 25–35 °C Time: TotalSugar: 53% [56]
hammer mill 3–24 h
Corn Stover Grinding Ammonia Recycle Temp: 170 °C Time: Cellulose yield: >95%, [57]
Percolation (ARP) 20 min Ammonia Hemicellulose removal:
concentration: 15wt% 60%
Lignin removal: 70–85%
Empty fruit branch of Grinding and screening Acid (e.g., acetic acid) Temp: 170 –190°CTime: Lignin removal: 59.5% [58]
palm tree (7–14 mesh) 10–20 min Acid Hemicellulose
concentration: 3 –7% hydrolysis: 53 6%

­ 2SO4, HCl, can be harmful because these acids are highly

H rare circumstances, including air in the system can help with
corrosive and require expensive materials for equipment delignification [49, 73].
construction.
Dilute acids primarily ­H2SO4 and HCl, are utilized at (a) Sodium or Calcium Hydroxide Hydrolysis
temperatures ranging from 160 to 220 °C for several minutes
to seconds to significantly redistribute and disrupt lignin Lime treatment is a method of improving alkaline
molecules in lingo-cellulose cell walls. Thus, acid treatment treatment by heating at a high temperature using lime.
can be classified into two types of dilute acid pre-treatment The procedure of lime pre-treatment is spraying it on
process: high temperature (temperature > 160 °C), and low material (biomass), and then keeping the material in pile
temperature (temperature ˂160 °C). In the case of dilute form for many hours to weeks. The biomass particle size
acid treatment at high temperatures, it can be performed in is less than10 mm. The increase in temperature shortens
a continuous flow process, whereas at low temperatures, it the contact time, which is also greatly influenced by the
can be conducted in a batch process with substantial solids type of lingo-cellulose, used in the reaction which is three
loading (10–40%) [41, 42, 46, 62, 69]. As a result, both hours at 85 ºC (wheat straw on oven dry basis) and one
processes have their drawbacks such as removing the acid hour at 120 °C (bagasse on oven dry basis) [31, 36, 74].
effluent and neutralizing the pH. Recently, phosphoric acid Pre-treatment efficiency is influenced greatly by time and
and volatile solvents such as acetone have also been used temperature, but the lime and water loading have little to
[49, 50, 68]. The procedure is mixing the sample with at least no impact [32, 47, 75–78].
85% phosphoric acid, incubating it at 120 rpm and 50 ºC for While having no negative effect on subsequent
one hr., and then centrifuging it. The results demonstrated hydrolysis, lime pre-treatment increases the digestibility
that phosphoric acid may remove substantial amounts of of lignin. Lime is widely available and is reasonably
hemicellulose, which is accompanied by partial removal of priced, which is an added benefit for cost-effective pre-
lignin. Additionally, the generation of inhibitory and toxic treatment. Furthermore, utilizing lime kiln technology,
chemicals has decreased significantly. Furthermore, acetone calcium can be recovered to calcium carbonate and utilized
removes practically all organic content, leaving simply as lime [47, 49]. Pre-treating lingo-cellulose with sodium
cellulose, sometimes known as ‘clean’ cellulose. Aldonic hydroxide is another common approach. It was observed
acid has also been reported to improve lingo-cellulose that combination of sodium hydroxide with dilute acid or
hydrolysis [70]. hydrogen peroxide increased delignification rate compared
to lime [65, 77]. According to Yoon et al., when sugarcane
Alkaline Pre‑treatment bagasse is treated with NaOH at 115 °C for 38 min, it
yields 92.8percent reducing sugar [79].
In comparison to other pre-treatment processes, this method
uses lower temperatures and pressures. As a result, it is (b) Ammonia Hydrolysis
possible to perform alkali pre-treatment at ambient con-
ditions. For effective hydrolysis research in morphology Ammonia pre-treatment methods comprise ammo-
showed that there is an increase in the porosity and outer nia recycles percolation (ARP), ammonia fibre explosion
surface when exposed to microorganisms or enzymes. In (AFEX) and others. The part on physicochemical prepara-
tion will cover ammonia fibre explosion (AFEX). Aqueous

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Table 3  Performance of acid-based pre-treatment

Biomass Initial mechanical pre-treatment Acid used Process parameters Results Refs

Wheat straw Grinding & screening (Size: Sulfuric acid Temp: 140 °C Glucose yield: 89.25% and; [71]
0.80–0.91 mm) Time: 30 min and; Xyloseyield:47.18%
Acid conc.: 10 ­dm3m−3
Corn Stover Grinding & screening (40 mesh) Hydrochloric acid Temp: 120 °C Total glucose yield: 85.9% [67]
& subsequent lime Time: 40 min Xylose yield:97% and;
treatment For Lime: Glucose yield increases upon
Temp: 60 °C enzyme loading
Time: 12 h and;
L/S ratio: 10:1
Reed stover Chopped Phosphoric acid Temp: 50 °C Ethanol yield: [68]
Time: 1 h >98.7% Ethanol and;Acid
Acid conc.: >85% conc.: 50.5 g/L
Corn stover Milling & screening (1.27 mm) Phosphoric acid For maximum glucose yield Max glucose yield: 85% and; [66]
Temp: 180 °C Max xylose yield: 91.4%
Time: 15 min
Acid conc.: 0.5%
For maximum xylose yield
Temp: 160 °C
Time: 10 min and;
Acid conc.: 1%
Rice straw Grinding & screening (<2 mm) Nitric acid Temp: 158.8 °C Xylose yield: 86.5% and; [64]
Time: 5.86 min and; Enzymatic digestibility: 83.0%
Acid conc.:
0.65%
Empty fruit Grinding & screening (7–14 Acetic acid Temp: 170–190 °C Lignin removal: 59.5% and; [72]
branch of mesh) Time: 10–20 min and; Hemicellulose hydrolysis:
palm Acid conc.: 3–7% 53.6%

ammonia is charged into a moderately pressurized flow that procedure [81]. Wheat straw was employed in the process,
goes through a biomass-filled reactor column in the ARP and the operating temperatures and pressures for the steam
process. The lignin and ammonia are recovered from liq- explosion were 200–220 °C and 15–22 bars, respectively.
uid fraction after reaction, and ammonia is recycled back The alkaline peroxide treatment was carried out for 5 h at
to reactor. Following washing, the cellulose and hemicellu- 50 °C with 2% H­ 2O2 at a pH of 11.5. As a result of the steam
lose-rich solid fraction is further processed. By soaking the explosion loss in hemicellulose, approximately 11–12%
biomass in aqueous ammonia at room temperature, aqueous lignin removal was observed, whereas the alkaline perox-
ammonia can also be utilized efficiently. Ammonia effec- ide post-treatment resulted in 81–88% removal of the native
tively eliminates lignin and considerably improves surface lignin, bringing the total removal of the original lignin from
area [57]. Because of the high cost of ammonia and the costs wheat straw to 92–99%.
involved with ammonia recovery, this treatment is not eco-
nomically feasible. However, the total sugar yield frequently Physico‑Chemical Pre‑treatment
outweighs the expense of pre-treatment [32].
Comparatively to chemical treatment, the physicochemical
(c) Alkaline Peroxide treatment also helps to increase the available surface area,
delignification (partial or total), and hydrolysis (partial or
Alkaline peroxide is another efficient approach for the complete). Additionally, these treatments reduce cellulose
pre-treatment of biomass. In this procedure, a solution of crystallinity and polymerization levels. Accordingly, these
NaOH and H ­ 2O2 with a pH of 11–12 is used to soak the techniques are among the most successful and promising
lignocelluloses for 6–24 h at room temperature [80]. Enzy- ones for industrial or manufacturing applications [32,
matic hydrolysis can be improved by delignification. Since 38]. However, there are some drawbacks connected with
this method produces very little furfural and hydroxymeth- these methods. Many of these treatments necessitate the
ylfurfural (HMF), it's better for digestion than pre-treatments presence of severe environments. Inhibitory compounds
employing diluted acids. In addition, alkaline peroxide can such as furfural are frequently generated because of severe
be used further to treat steam-exploded biomass in a separate

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circumstances, which have a deleterious impact on the an acid, and addition of C ­ O2 or S­ O2 or H

­ 2SO4 [typically
subsequent hydrolysis and fermentation processes. 0.30–3.0% (w/w)] in a steam explosion can reduce
temperature and residence time, thereby decreasing the
Organosolv Pre‑treatment generation of inhibitory chemicals and leading to the total
elimination of hemicellulose [77, 80, 84, 85]. Hence, steam
In this pre-treatment, a broad range of various organic explosion operation parameters should be chosen in such a
solvents, including alcohols, ketones, esters, organic way that excessive cellulose degradation is prevented. The
acids, glycols, ethers and phenols can be utilized. To treat use of extremely severe conditions may have resulted in
lignocellulosic material, organic or aqueous organic solvents poorer enzymatic digestibility of lignocelluloses following
can be employed with or without the addition of catalyst like, steam explosion. In steam pre-treatment, "severity factor"
salicylic, acetylsalicylic and oxalic acid [80] at 90–250 °C (log), refers to a measure of the pre-treatment’s severity.
temperature [36]. Solvents and water in varying amounts are In this severity factor the temperature and the duration
added to the biomass, which is then heated to dissolve the of the pre-treatment are combined as given below in Eq. 1,
lignin, leaving a reactive cellulose cake [80]. The operating
T − 100
[ ( )]
time for this pre-treatment is 90 min. at 120 °C for grasses log = log t.exp (1)
14.75
and it is 155 min at 220 °C for woods, with a residence time
of 25 to 100 min. where, T is the temperature in °C and.t is the time in minutes.
Depending on the substrate, catalyst concentration can Aside from steam explosion, the severity factor can
vary from 0.8 to 1.7% and alcohol concentration from 25 to also be applied to hydrothermal acidic hydrolysis and
74% (v/v) (da Costa Sousa et al., 2009). Isolation of lignin conversion. The use of steam explosion is confined to
as solid substance and carbohydrate as syrup (both showing hardwood and agricultural residues. The main drawbacks
promise as chemical feedstocks) and recovery by distillation of the steam explosion method include partial hemicellulose
can be obtained using organosolv pre-treatment [82]. degradation and the creation of poisonous chemicals such
However, to make the pre-treatment more cost- as furfural, phenolic compounds, and others, which impair
effective, the costs of solvents and that of recovery must be the subsequent hydrolysis and fermentation processes [53].
considered. Particularly, the solvents should be evaporated, The type and amount of hazardous chemicals generate
condensed, and subsequently recycled to reduce the total during steam explosion are determined by the feedstock and
process operational costs. However, because some solvents the severity of pre-treatment. According to a study conducted
are inhibiting, the presence of solvent residue in pre-treated by Ballesteros et al., the adoption of a thermotolerant yeast
cellulose may be detrimental to enzymatic hydrolysis & strain can alleviate the problem to a certain extent [86].
fermentation. For economic considerations, alcohols with
low molecular weight (e.g., methanol and ethanol) may Ammonia Fibre Explosion (AFEX)
be preferable over higher molecular weight alcohols (e.g.,
ethylene glycol) with high boiling point. Due to ethanol’s The Ammonia Fibre Explosion or AFEX is almost like
inhibiting effect on enzymatic hydrolysis, it should be steam explosion. Biomass with the desired moisture
separated from the treated lingo-cellulosic biomass prior to content is treated with anhydrous ammonia at high pressure
enzymatic hydrolysis. However, more research is needed to (17–21 bar) and moderate temperature around 60–100 °C,
understand how organosolv pre-treatment condition such as followed by a rapid release of the pressure [48]. In the
solvent type influences cellulose crystallinity and swelling AFEX process, the liquid ammonia dosage is around
[36]. When lignin is oxidized, inhibitors are generated, and 1–2 kg ammonia per kg biomass (on oven dry basis) at90 °C
a large amount of carbohydrates, such as sugar, is lost. temperature and 30 min residence time. In flow-through
mode ­NH3 solution (5.0–15.0%) is passed through a column
Steam Explosion reactor packed with lignocellulosic materials a fluid velocity
of 1 ­m3/s for two minutes at high temperatures (160–180 °C)
The steam explosion eliminates most of hemicellulose and with residence times of 14 -15 min inside the reactor.
makes the cellulose more sensitive to hydrolysis. In this Following the reaction, rich solid fraction is separated that
approach, lignocellulosic materials are treated with high is the cellulose and hemicellulose and ammonia recovers
pressure steam, which is followed by a quick reduction of when liquid fraction is passed to the evaporator, which also
pressure, causing the biomass to decompress explosively. separates lignin and sugar. Because ammonia is separated
In most cases, prior to air pressure exposure; 160–260 °C and recycled, this technology is also known as the ammonia
temperature (corresponding pressure 7–50 kg/cm2) steam recycled percolation (ARP) process. Pre-treatment with
explosion of the material is done from few to several minutes AFEX can boost the saccharification rates of a variety of
[32, 35, 80, 83]. At high temperature, water functions as herbaceous crops and grasses [31, 35, 46, 48, 87, 88]. The

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cost of ammonia, particularly ammonia recovery ultimately acids [47]. The LHW pre-treatment increases the surface
determines the cost of this procedure [75]. area of cellulose that is accessible and susceptible to
In comparison to other procedures, however, AFEX enzymatic hydrolysis, making it more accessible to them.
capacity to reduce the creation of sugar breakdown products The advantage of LHW over steam pre-treatment includes
at moderate temperature and pH value makes it superior more pentosan recovery and less generation of inhibitors
to other methods. Enzymatic hydrolysis doesn't require (e.g., furfural). The elimination of xylan using a percolation
neutralization of the treated biomass, as a considerable reactor or by adding a base during the process minimizes
amount of ammonia may be recovered, and the residual the production of inhibitors and the degradation of xylose.
ammonia can act as a nitrogen source for the microorganisms To enhance enzymatic digestibility by LHW pre-treatment,
[48]. As a result of these modifications, the delignification processing temperature, pH, and duration must be regulated
process and biomass fractionation have improved. [31, 36, 93–97]. In this procedure, biomass is treated in hot
water for around 15 min at increased temperatures ranging
CO2 Explosion from 200 to 230 °C.
This procedure dissolves around 40–60% of the entire
This approach is like AFEX and steam explosion, with the biomass, with 4–22% of the cellulose, all the hemicellulose
exception that in ­CO2 explosion, pressurized ­CO2 is charged and 35–60% of the lignin being eliminated. LHW reactors
into the reactor, and then pressure is suddenly dropped after are configured in three different ways, namely flow-through,
a few seconds. As a result, carbonic acid is produced and the counter current and co-current. In co-current pre-treatment,
rate of hydrolysis is improved although the yield becomes (biomass in liquid slurry form) of roughly 16% solids is
significantly lower than that of steam explosion or AFEX heated to 140–180 °C and kept for 15–20 min, followed by
[81]. cooling and heat recovery. In counter current pre-treatment,
Another way to use ­CO2 to pre-treat lingo-cellulose is biomass slurry flows in co-current while water flows counter
as a solvent in extraction at supercritical conditions. The current in a jacketed reactor. Hot water is forced over a
supercritical fluid shows the properties of both liquids and static layer of lingo-cellulose in a flow-through reactor at
gases above critical temperature and pressure. Supercritical temperatures and pressures ranging from 180 to 220 °C and
­CO2 and water in the biomass create a carbonic acid mixture 24 to 28 bar respectively. In both flow-through and counter
that helps hemicellulose hydrolysis by providing a weak acid current modes, temperatures, pressures, and residence
environment. Other than temperature and pressure, the most durations are comparable. At the same severity factor, batch
essential factors for this pre-treatment are moisture content systems removed less hemicelluloses and lignin from corn
and pre-treatment time. According to the study, treating stover than flow through system [32, 47, 77].
rice husk with supercritical ­CO2 at 80 °C temperature and
270 bar pressure for 10 min reduces lignin concentration Ionic Liquid Approach (IL)
by up to 90.6% [89]. According to the techno-economic
analysis reported in [89], this approach is more efficient Ionic liquids are composed primarily of ions and having low
and cost-effective than acid pre-treatment. Though the melting points (less than100 °C), great thermal stability, and
energy required for ­CO2 conditioning raises utility costs. low vapour pressure [98]. Ionic liquids containing anions
However, the operating costs of dilute acid pre-treatment such as halide, acetate, formate, and phosphate can be
are substantially greater due to the inability to recycle the employed as a dissolving medium for carbohydrates such
reagents together with the costly biomass recovery and as cellulose [97, 99, 100]. Polar solvents absorb microwave
detoxication procedure [89–92]. irradiation and thus can be heated more quickly than
non-polar solvents that have little or no ability to absorb
Liquid Hot Water (LHW) microwave radiation. The high polarity of ionic liquids is
an added benefit because microwave heating is based on the
The digestion of plant biomass (lignocellulosic)in liquid hot polarization of molecules.
water (LHW) is prominent hydro-thermal method applied for A recent study reported that when ionic liquid treatment
the pre-treatment of biomass. High-pressure water can enter is aided by microwave heating, the concentration of ILs in
the biomass and hydrate cellulose. It removed hemicellulose a solution can be greatly enhanced. The cellulose can be
and lignin fragments. There is no need for corrosion-resistant regenerated by addition of an anti-solvent (e.g., distilled
biomass in hydrolysis reactors in this method, and no water, alcohol, or acetone) resulting in an environmentally
chemicals are required. There is no size reduction required benign and low energy consumption method as compared to
in liquid hot water (LHW). The technique necessitates other dissolution techniques [101, 102].
significantly less chemical use for the neutralization of the Due of these features, the ionic liquids like,
generated hydrolysate, which contains released organic 1-butyl-3-methylimidazolium chlor ide and

13
 Journal of Polymers and the Environment

1-ethyl-3-methylimidazolium acetate are ideal alternative optimal time. To neutralize the contents, they were filtered,
agents for pre-treating lingo-cellulose. The experimental and the solid residues were vigorously rinsed to achieve a
data reveal that cotton celluloses regenerated using micro- neutral state. This approach improves enzyme accessibility
wave aided ionic liquid pre-treatment may be hydrolysed during saccharification because it degrades lignin sheath
much faster than those without microwave irradiation, and better than steam explosive alkaline treatment and has
the degree of polymerization of cellulose is significantly lower energy consumption [109–111]. Batch mode trials
reduced [103]. The ionic liquid can also be utilized to insert using ultrasonic-assisted pre-treatment of cassava chips
nanoparticles into lignocellulosic biomass cell walls, which have so far proven promising for ethanol production
can then be chemically functionalized [104]. The incorpora- on a modest scale. This pre-treatment, when combined
tion of microparticles with a high surface-to-volume ratio with simultaneous saccharification and fermentation, is
can open-up entirely new possibilities in pre-treatment. effective in breaking corn starch structure and increasing
This approach entails saturating woods with an ionic glucose concentration before or after liquefaction under
liquid at room temperature, then exposing them to an certain sonication conditions. It reduces fermentation time
aqueous solution of nanoparticles [105]. For this purpose, by nearly 24 h while considerably increasing ethanol yield.
silver and gold nanoparticles have been investigated thus far However, when the energy consumption scenarios of batch
[104]. This preparation is based on the expansion of wood mode and continuous flow systems are considered, the
cells using an ionic liquid and the shrinkage of wood cells continuous flow system is determined to be more suitable
by simply rinsing with deionized water. The hydrogen-bond for industrial-scale applications. Considering experimental
network, which is the backbone of the lignin structure, is design which might use more energy in different steps of
disrupted by this overall expansion and contraction utilizing experiment such as energy consumption in pre-treatment
ionic liquid. costs may affect plant finance [106, 107, 112, 113].

Combination of Pre‑treatments
Microwave‑Assisted Pre‑treatment
The traditional pre-treatments discussed earlier have various
limitations, and to overcome them some improved and The microwave heating is a more effective method of
effective approaches have lately been implemented. These enhancing enzymatic hydrolysis than conventional heating.
techniques include sono-assisted and microwave-assisted The method outperforms chemical pre-treatment with
processes in addition to the integration of nanoparticles conventional irradiation [114, 115]. Although xylose
and the use of activated carbon via photolysis. Thermal cannot be recovered during the microwave-aided alkali pre-
pre-treatment in combination with acid, alkali, oxidative, or treatment process, it can be recovered as crystalline xylose
alkaline oxidative treatments has proven to be an extremely during the microwave-assisted alkali, acid, and ­H2O2 pre-
successful pre-treatment method. treatment processes [114]. It is performed in many ways
such as microwave-assisted alkali, microwave-assisted acid,
Ultrasonic‑Assisted Pre‑treatment and alkali treatment, and microwave-assisted acid, alkali,
and ­H2O2 combined pre-treatment [115, 116]. Combined
The use of ultrasound as a pre-treatment tool is a relatively effect of microwave and chemical disruption using dilute
new approach that is thought to have the potential to sulphuric acid of hemicellulose gave rise to structural
increase the yield of fermentable sugars. Depending alteration in bagasse [59].
on the frequency, it is classified as power diagnostic Microwave treatments are also considerably more digest-
ultrasound (1–10 MHz), high-frequency ultrasound ible of cellulose than traditional heating, although they are
(100 kHz–1 MHz), and ultrasound (16–100 kHz) [106]. unable to entirely breaking down refractory structures such
When a low-frequency wave travels through an aqueous as switchgrass. Therefore, the fermentable sugar yield is
medium, it causes huge bubbles to form due to cavitation, reduced in comparison [101]. According to [115], micro-
and a hydro-mechanical shear force to form in the bulk wave-aided alkali pre-treated substrate requires less enzyme
liquid due to the quick collapse of the bubbles, causing the loading, takes a lesser time to ferment, and yields more etha-
coarse particles in the liquid to be disrupted into smaller nol than traditional alkali pre-treatment [115]. To pre-treat
particles. If enough energy is produced, the hydrogen rice-straw, microwave-assisted acid, alkali, and hydrogen
bonds in the crystalline structure of cellulose can be peroxide combination pre-treatment is more successful
disrupted [106–108]. Sono-assisted alkali pre-treatment than microwave-assisted alkali pre-treatment because it has
entails dilution of dried and sieved samples into a 2% the highest hydrolysis rate, as well as high glucose and low
NaOH solution, followed by ultrasound treatment for an xylose content. In some circumstances, this xylose can be

13
Journal of Polymers and the Environment

retrieved during this pre-treatment, whilst in others, it can- Biological pre-treatment in combination with dilute acid
not [115]. pre-treatment has also been explored and it has proved as
Pre-treatments such as a steam explosion or AFEX an effective tool for pre-treatment. Acid pre-treatments that
involve high temperatures [46, 49, 117] which exploit energy are used nowadays are often dangerous and not economically
sources and hence raise costs. To address this constraint, viable. Less energy-intensive biological treatments utilizing
an additional process that employs a compound (such as fungi, on the other hand, necessitate mild conditions and
glycerine) with a high dielectric constant when mixed with dramatically reduce lignin content by destroying the
water, is used, and can absorb microwave irradiation while hemicellulose-lignin bond [122, 123].
also lowering the system's vapour pressure. This system A study by [124] shows, raw and bio-pre-treated water
enables the experiment to be carried out at atmospheric hyacinth with Antrodia sp. 5898 (brown rot fungus) or
pressure [118]. Echinodontium taxodii (white rot fungus) in combination
with 0.25% sulphuric acid at varying temperatures (25, 80,
Activated Carbon Approach and 100 °C) for 15–60 min, proved to be an effective method
to improve enzymatic hydrolysis and bio-ethanol production
Activated carbon is a micro porous type of carbon that has from water hyacinth (Table 3). At the same conditions, the
been activated by a controlled oxidation process and has a reducing sugar yield from enzymatic hydrolysis of co-treated
large surface area for adsorption and chemical reaction. The samples increased 1.13–2.11-folds compared to acid-treated
use of activated carbon in the processing of lignocellulosic samples. Table 4 shows a summary of various methods used
material is a novel method. For improved yield, activated for lignin pre-treatment.
carbon can be utilized to modify acid or alkaline treatment.
It is also very good at eliminating inhibitors produced during Natural Deep Eutectic Solvents Process
pre-treatment. The process includes washing and drying
activated carbon granules, adding activated carbon to the NADES is bio-based DESs (Deep Eutectic Solvent)
liquid fraction at room temperature, and separating activated composed of natural products such as amides, sugars,
carbon with adsorbed inhibitors from the liquid fraction alcohols, and amino acids. DESs are eutectic mixtures
[119]. The amount of one of the hydrolysis inhibitors, generally consisting of a hydrogen bond donor (HBD)
furfural, can be greatly reduced by activated carbon and a hydrogen bond acceptor (HBA), which combine via
treatment, resulting in a higher ethanol yield. Fermentation hydrogen bond (H-bond) interaction. Both HBD and HBA
on the activated carbon pre-treatment entire slurry will boost are selected based on their ability to form strong hydrogen
sugar usage while lowering production costs [119]. There bonds and do not involve any chemical reaction. In NADES,
is also a unique pre-treatment method reported that uses the HBD is a low molecular weight organic compound with
an alkali solution assisted by photo-catalysis [112]. It is a H-bond donating group (amine, carboxylic acid), while the
modified alkaline treatment in which nano-TiO2 produces HBA is high molecular weight inorganic salt with a strong
hydroxyl and superoxide radicals when exposed to light, ionic bond (choline chloride). The combination of these two
resulting in the formation of radical sites on the substrate components by mixing them in a specific molar ratio results
and improved degradation. The time required for photo- in a eutectic mixture with a lower melting point than either
catalysis is critical in this process. The cellulose content component alone. The resultant liquid is used as a natural
of the pre-treated sample increases due to this process, and deep eutectic solvent, with advantages over conventional
the alkali dosage required for pre-treatment is reduced. solvents, such as improved solubility and reduced toxicity.
However, additional research into this technology is needed When lignocellulosic biomass is treated with NADES,
to improve it [112, 120, 121]. a simple dilution procedure was used to precipitate soluble
In combination of thermal and alkaline oxidative pre- lignin from the NADES extract; after extraction the recovery
treatment, biomass enzymatic digestibility was 13 times of NADES reagent from water solution and it was removed
more than that of untreated biomass. By carbon dioxide from residual liquid using rotary vacuum evaporation at
carbonation, around 21% of the lime added could be 60 °C, after lignin removal from the interaction between
recovered after the oxidative lime pre-treatment was biomass and reagent. After that the recovered NADES
completed. Thermal pre-treatment alone cannot remove reagent and water were both utilized in the next cycle of
lignin from biomass that is high in lignin; therefore, oxygen biomass treatment and lignin precipitation without any
as an oxidant must be added during the pre-treatment to alterations [135, 136].
increase the enzyme digestibility. Because of the low The recovery and recycling of DES after pre-treatment is
working temperature i.e., 150 °C, little sugar degradation is one of the most pressing concerns for DES-based biorefinery
also noticed during the process [49]. [137]. However, the most common approach for DES recov-
ery after biomass pre-treatment is moisture evaporation,

13
 Table 4  Summary of various methods used for lignin pre-treatment
Pretreatment Method Chemical and substrate used Reaction conditions Potential sugar yield Formation of inhibitor Type of inhibitors Refs

13
Acid (weak) HCl, ­H2SO4, weak acid treat- Temp: >160 °C< Hemicellulose removal, lignin High Aliphatic carboxylic acids, [44, 47, 50, 59, 125]
Acid (strong) ment is especially suitable Pressure: atmospheric Structure alteration phenylic compound, furans
for biomass with low lignin Time: depends upon the hydrolysis of cellulose and etc
content temperature hemicellulose by treatment
with strong acid
Alkaline Sodium Hydroxide, Calcium Temp: 50- 121 °C, Removal of lignin and some High Acetic acid, hydroxy acids, [73, 126]
hydroxide, Low lignin con- Time: 15 min part of hemicellulose dicarboxylic acids, furfural,
tent material (Wheat straw, to 24 h (Depends on tempera- and phenolic compounds
corn stover, ture) Pressure: 0–1 bar
rice straw etc.)
Organosolv Organic solvents (Methanol, Temp: 90- 250 °C Removal of lignin High (Depends on solvent) Aldonic and aldaric acids, [82, 127]
butanol, acetic acid, glyc- (Depending furoic acid, phenolic acids,
erol, etc.), Woody biomass upon biomass), Time: 25–100 acetic acid (Depends on
(Poplar, spruce) Wheat min Pressure: atmospheric solvent)
straw, rice
Straw etc
Steam Explosion Sulfuric acid, S
­ O2, All types Temp:160–260 °C Removal of hemicellulose Moderate Acetic acid, minor amounts [32, 83]
of biomasses Pressure:6.89—48.3 bar and alteration of lignin of furan aldehydes
Time: several seconds to structures
few minutes
AFEX Ammonia All types of Temp: 60- 100 °C Removal of lignin and recrys- High Acetic acid and furan [46, 48, 128, 129]
biomasses Pressure:17–21 bar tallization of cellulose aldehyde
Suitable for all types of Time: 5- 10 min
biomass
LHW Especially suitable for Temp: 100- 250 °C Removal of hemicellulose High Acetic acid, furan, and [36, 94, 96, 97, 130]
biomass with low lignin Pressure: furfural
content 20–30 bar Time: several
minutes to hours
Activated Carbon Suitable for all types of – Modify acid or alkaline treat- High No (Generally used to remove [112, 119–121]
biomasses ment for better yield inhibitor)
Ionic liquid Ionic liquids, Suitable for all Temp: atmospheric Dissolution of cellulose High to moderate Depends on solvent and [98–100, 104, 105, 129, 131]
types of biomasses and alteration of lignin condition
structures
DES All types of biomasses Temp: 60–140 °C Removal of hemicelluloses – [99, 132]
Time: 1–9 h and lignin
NADES Rice straw Temp: 60 -120 °C Time: Removal of lignin CC:LA [52, 133]
minutes to hours CC: Gly
Pressure: 1 bar
Journal of Polymers and the Environment
Journal of Polymers and the Environment

which cannot eliminate the contained biomass degradation the recovered DES was used. With no further purification,
products in DES any further [135, 138]. To operate on a vast recovered DES was then used to pre-treat raw eucalyptus
scale, membrane-based approaches should be explored for four times at 110 °C for six hours.
such recovery tasks due to the robustness and low cost [139]. The recyclability of natural deep eutectic solvents
The volume of DES recovered during the separation process (NADES) at low-vapour pressure could provide a challenge.
is also an important criterion that has a significant impact According to [147], DES can be regenerated using vacuum
on the biorefinery’s operational costs. However, the greatest evaporation. However, [136], managed to separate the
potential feature of DES systems is their effective recycling NADES from the residual liquid fraction after lignin
[140], which is one of the most significant characteristics separation, the residual lignin fraction was subjected to
associated with DES performances. rotary vacuum evaporation at 60 °C. Both the NADES
A recent study found that recycling enzymes and DESs reagent (Choline Chloride-lactic acid) and the recovered
are promising combination because the entire process can water were reused in the next cycle of biomass pre-
be operated at low cost [141], cell immobilization might be treatment and lignin precipitation, resulting in significant
achieved with the use of DES, cells and enzymes in a whole cost savings. Aside from that, the NADES solvent was
system, allowing for a more efficient recycling process to effectively recovered and recycled at least three times in
be achieved [142]. successive biomass pre-treatments without reducing its
Hayyan [143], reported that a significant conversion to effectiveness. With similar results, the NADES (Choline
the product was achieved using newly generated ChCl-DES Chloride-glycerol) was reused for three more extraction
and subsequent recycling on acidic crude palm oil, while the cycles after the solute was recovered using anti-solvent and
third recycling run showed a slight drop. This indicates that the water was removed via vacuum evaporation [148]. One
the DES catalyst is highly active for esterification reactions of the disadvantages of DES, according to [147], is mixture
because no extra ChCl-DES was added during the recycling instability. However, it was reported in another study in the
runs. To produce biodiesel from palm oil of low quality, same year that the synthesized NADES remained stable at
the same authors applied phosphonium-based DES (1:3) as room temperature for weeks without precipitation [149].
a catalyst. With only a 10% drop in conversion yield, the A comparison between advantages and disadvantages of
system was able to be used for four cycles in total [144]. pre-treatment methods of various biomass is presented in
This demonstrates that DESs can catalyse the esterification Table 5.
processes.
In a study by [145], rice straw was pre-treated with
ChCl, formic acid, and acetic acid (1:1:1). Both DES and
cellulose could be reused for five continuous cycles, while Description of the General Method of Lignin
the hydrolysate was used in butanol fermentation to produce Extraction
9.5 ­Gdm−3 and 0.25 G ­ g−1 butanol, respectively. The DES
was found to be effective in the enzymatically catalysed As already known, it is impossible to isolate lignin in its
generation of biodiesel. natural (unaltered) state since extreme procedures for
According to [146], the pre-treatment was carried out in separating lignin from cell walls and cellulose are required,
the reaction vessels with a biomass content of 10 weight % which partially alters its native structure [156]. Although
(2 g of dry biomass and 20 g of DES or lactic acid). The pre- attempts have been made to simplify lignin isolation
treatment temperature was gradually raised from ambient procedures and make them more environmentally benign,
temperature to the target one, which was maintained for 6 h. as well as to obtain polymers with more maintained natural
Pre-treatment produced a dark brown fluid, and the acetone/ structure [157]. The structure of isolated lignin varies due
water anti-solvent (100 mL) was added to the mixture and to different feedstocks, extraction techniques, and extraction
agitated for 6 h. The solid fractions and DES soluble fraction severity. On a wide scale, lignin is produced by the pulp and
was washed three times after vacuum filtering with 50% paper industry, as well as numerous biorefinery processes,
acetone/water. In addition to filtration, the acetone from such as hydrolysis/fractionation by hot water, alkaline, or
the liquid fraction was removed by heating at 50 °C and enzymes dilute acid, soda pulping, sulphite pulping and kraft
filtering the concentrated suspension to retain the solids pulping as outline shown in Table 6 [158].
fraction, which was characterized as regenerated lignin. Lignin used above is derived from several material
While this was going on, the concentrated solution was described in Table 7 below, shows different material such
heated in a vacuum oven at 65–70 °C temperature for 24 h as mustard stalk, Natural biomass, Triticale straw, rice straw
to remove water before weighing to evaluate the amount of etc. for the fractionation of lignin using various treatment
DES recovered after the pre-treatment. To test the impacts of processes such as formic acid, acetic acid, and water (FA/
DES recycling on the pre-treatment efficiency of Eucalyptus, AA/H2O), PFA/PAA and bleaching; FA/AA/H2O mixture

13
 Journal of Polymers and the Environment

Table 5  Advantages and disadvantages of various pre-treatments methods

Types of Pre-treatments Advantages Disadvantages References

Mechanical Pre-treatment Easy handling, Excessive energy usage [150]

Regulation of final particle size, and;
Intensive decrystallization
Acid pre-treatments Mild conditions, High-priced acids, inhibitor by-products [4, 150–152]
Can achieve at higher reaction rates, formation, expensive corrosive resistant
Less toxic products formation, and equipment, low concentration of reducing
High sugar yields sugars, neutralizing salts must be disposed
of, more costly pre-treatment compared
to another pre-treatment method such as
AFEX, and; recovery of acid
Alkali pre-treatment Ambient conditions, Expensive alkaline catalyst, Not suitable for [4, 151, 152]
Effective lignin removal, and; large-scale plants, Inhibitor generation,
Reduced sugar degradation as compared to and; Effectiveness decreases as lignin
acid pre-treatment content of biomass increases
Organosolv pre-treatment Effective delignification, Expensive Solvent recovery, [150, 151]
Hydrolyses lignin and hemicellulose Inhibitor formation, and;
Use or handling of hazardous organic
solvents
Steam explosion Energy efficient, By-product inhibition, [150, 152]
Cost effective, Degradation of xylan,
No recycling cost, Formation of toxic compounds, and;
Less use of chemicals, Partial degradation of hemicellulose
Less input of energy, and;
Obtain higher yield of glucose and
hemicellulose (within two-step process)
Ammonia Fibre Explosion (AFEX) Low inhibitor formation, Ammonia toxic in nature and has higher [4, 150, 151]
Reaction with lignin is highly efficient and energy cost,
selective, and; Method is Ineffective for lignin-rich biomass,
High efficiency for low lignin content and;
biomass e.g., herbaceous material Changes the structure of lignin
CO2 explosion Low-cost availability, Requires high pressure [150, 153]
No inhibitory compounds are formed,
Non-combustible,
After extraction it is simple to recover and
acceptability to the environment, and;
Toxins are not produced
Liquid Hot Water (LHW) Catalyst is not required, Low costs High energy and water usage, and; [4, 150]
solvents are advantageous for large scale Toxic chemical production
applications, Not necessary to reduce the
size of biomass, Mostly no chemicals
required, and; Corrosion-resistant materials
not required
Biological pre-treatment Low energy required, Slow hydrolysis rate, [150]
Effective delignification, and; Ineffective for commercial application, and;
Moderate environmental conditions Loss of cellulose
Microwave assisted pre-treatment Suitable for various softwoods Requires high temperature, [152]
Nonuniform biomass heating,
Energy and time-consuming, and;
Requires big irradiator for large scale
biomass treatments
Ionic liquids Dissolve high solid loadings, and; mild Expensive in nature and solvent recovery, [154]
reaction conditions, Poor biodegradability,
Difficult to synthesize with multi step
reactions and purification,
Arduous to recycle
Costly solvents, and;
Inhibitory effect on enzyme activity

13
Journal of Polymers and the Environment

Table 5  (continued)
Types of Pre-treatments Advantages Disadvantages References
NADES Easy to prepare, Limited research [155]
Simplified purification procedures, and
utilisation of recycled materials,
Biodegradable and Biocompatible,
Less expensive than ILs,
Non-toxic,
Low cost, and;
Eco-friendly

at atmospheric pressure. Later treated pulp improved in an The use of alternative solvents in biorefinery processes
efficient and selective manner using peroxyacid (delignified is a growing trend. According to Cicci et al. [183], novel
fibres were filtered), then it was facilitated by chlorine free solvent systems and process technologies based on them
bleaching (used to remove lignin completely), whereas after are increasingly being developed to address the two major
treating with various materials only isolation of lignin was challenges that biomass present. Firstly, the fractionation of
observed in natural biomass resources. Thus, lignin obtained lignocellulosic materials, which constitute today’s largest
using lignocellulosic biomass enhances lignin into value biomass pool, secondly, microalgae which constitute tomor-
added products, chemicals and fuel enhancing overall indus- row’s biomass with the greatest growth potential.
trial plants operation cost effectivity [171]. According to the scheme by Kumar et al. of NADES
Biorefinery processing using alternative solvents includ- based lignocellulosic biorefinery [136], NADES based on
ing NADES, NADES assisted integrated waste biorefinery choline-chloride are hydrophilic and have a greater polarity
approach (Fig. 3) . A variety of separated products are syn- than water. Their polarity can be adjusted by varying the
thesized in biorefinery plant that combines biomass fraction- amount of water in the NADES formulation. They can
ation & bioconversion processes. The production of value- solubilise lingo-cellulose because of their polarity [183].
added chemicals, transportation fuels, and power make use To the best of our knowledge, no integrated approach for
of these products. Pre-treatment is regarded as one of the NADES based orange peel waste (OPW) biorefinery has
most important processes in bioprocessing for the manu- been established. To demonstrate the possibility of using
facture of transportation fuels. In a biorefinery, an efficient NADES as a multifunctional and unique solvent for the
pre-treatment procedure increases the overall downstream valorisation of OPW via the green integrated biorefinery
processing processes [27]. According to Chew& Metz [175, approach, preliminary screening of NADESs for the
176], a biorefinery is a facility that incorporates all forms of valorisation of OPW was carried out in two methods which
biomass feedstock conversion processes into various kinds is as follows:
of biofuels and bio-chemicals. A biorefinery is a comprehen-
sive, efficient, and adaptable way of converting accessible • The utilization of NADES as a catalyst in the OPW
biomass into a diverse range of value-added bio-based prod- catalysed synthesis of (R)-phenyl ethanol, a valuable
ucts through the use of several processes and this concept of chiral building block and synthetic intermediate
biorefinery arose in response to the global energy crisis and in the fine chemical, agrochemical industries and
the effects of climate change caused by intensive industri- pharmaceutical.
alization [177, 178]. The circular economy model strength- • The application of NADESs as a solvent for extracting
ens with the exponential growth of the biorefinery concept high valued bioactive chemicals (polyphenols and
[1, 179]. In the circular economy concept, lignocellulosic D-limonene) and proteins including the industrially
resources are used to produce bio-based products which are essential enzyme pectin methyl esterase from the OPW.
collected, repurposed, and reused [180]. The development of
integrated biorefinery from the standard biorefinery system Depending on the outcomes, an integrated biorefinery
can be an interesting solution for various valued product technique utilizing a single NADES in a multi-step process
generation by the processing of winemaking by-products as was proposed [184].
raw materials [181]. An integrated biorefinery is constantly In another case, to investigate the application of spent cof-
emerging with various technologies that enable the conver- fee grounds (SCG) in a biorefinery system to produce bioac-
sion change of waste into a slew of commercially significant tive compounds with antioxidant action as well as advanced
products and various forms of energy with nominal waste biofuels, microwave assisted NADES extraction technique
and pollution [182]. was proposed. In this the leftover NADES extracted SCG
was utilized for butanol generation via ABE fermentation

13
 Table 6  Industrial methods for extracting lignin with different lignin sources
Lignin sources Lignin extraction methods Lignin extraction conditions/procedures Lignin and features References

13
Lignin from pulp and paper making Kraft pulping Temp.150–180 ℃, water, ­Na2S and NaOH, Kraft lignin: low purity, -HS group [159]
industry (1.5-3wt%S) and oligomers with highly
condensed structures
Sulfite pulping Temp. 140–170 °C, Ligno-sulphonate low purity, -SO3 group [159]
Sulphite/Bisulphite salts (e.g., M ­ gSO3, (4–8 wt% S) and oligomers with highly
­Na2SO3, ­NaHSO3, ­(NH4)2SO3, ­CaSO3) condensed structures
and water
Soda pulping Temp. 160–170℃, NaOH (Anthraquinone) Soda lignin: low purity sulphur free lignin [160]
and water
Organosolv pulping Temp.100–110℃, Alcohol or alcohol/water Organosolv lignin: High purity sulphur free [161]
mixtures, ­H2SO4, Acetic acid, Formic lignin
acid and water
Hydrolysis of lignocellulosic biomass with Temp.120 °C- 300 °C, upto5 wt.%H2SO4, Lignin oligomers: partial preservation [162]
dilute acids HCl, HF or H ­ 3PO4 of β-O-4linkages with less condensed
structures
Hydrolysis of lignocellulosic biomass with Two-step’s treatment: Klason lignin: Condensed structure highly [163]
concentrated acid i) Temp.20–30 °C, degraded oligomers
Concentrated mineral acid (e.g.,72%
­H2SO4)
ii) Temp.121 °C, diluted
Sulphuric acid
Lignin from biorefinery processes Hydrolysis of lignocellulosic biomass with Temp.40 °C-160°C, Oligomers and lignin monomers [72, 164]
alkali Ca(OH)2,NaOH,NH4OH and water with low condensed structures
Hydrolysis of lignocellulosic biomass with Temp.30–60 °C, cellulase, water and Enzymatic lignin residue:low purity, less [141, 165]
Enzyme hemicellulose, addition condensed structures and large variety
pre-treatments (e.g.,
steam explosion, dilute acid, ammonia fibre
explosion etc.)
Reductive or oxidative fractionation of Temp. 150 °C-250 °C, H ­ 2O or organic Highly depolymerized and deoxygenated [166]
lignocellulosic biomass solvents, and; H ­ 2 or ­H2-donating lignin oil and lignin-derived acids
solvents or oxidants (e.g., ­O2, ­O3,
H2O2)
Combined pre-treatment methods Temp. 25 °C-200 °C, water or organic Lignin oligomers or lignin or: with less [167, 168]
solvents, e.g., mechanical milling condensation structures, large variety
combined with acid catalytic fractionation,
deacetylation with
mechanical refining
Lignin from mechanical pre-treatment At room temperature, extensive ball Milled wood lignin (MWL): low purity
milling, solvent extraction low lignin yield, resembles native lignin
structures,
Journal of Polymers and the Environment
 Table 6  (continued)
Lignin sources Lignin extraction methods Lignin extraction conditions/procedures Lignin and features References

Lignin used for structure analysis Lignin from ball-milling, cellulolytic Two Steps: Cellulolytic enzyme lignin (CEL): low [169]
enzyme hydrolysis of biomass i) Ball-milling lignin yield, relative low purity resembles
ii)Hydrolysis by cellulase & hemicellulose, native lignin structures,
40 °C-60 °C, water Buffer (pH: 4–5)
Lignin from ball mining, cellulolytic Three Steps: Enzyme mild acidolysis lignin (EMAL): [170]
enzyme hydrolysis, and mild acidolysis i) ball-milling Relative high purity, low lignin yield,
of biomass ii)Hydrolysis by cellulase & resembles native lignin structures,
hemicellulose, 40 °C-60 °C, water,
Buffer (pH: 4–5);
Journal of Polymers and the Environment

iii) Mild acidolysis by HCl, dioxane/water,

80 °C-90 °C

Table 7  Lignin extraction with various lignocellulosic biomasses

Material used Formic acid/Acetic acid/ Peroxy formic acid/peroxy Bleaching (pH, temperature, Isolation (Ratio, Reaction process of References
Water (Ratio, temperature, acetic acid treatment (PFA/ time) temperature, time) PFA/PAA treatment
time) PAA) (ratio, temperature,
time)

Mustard branches, Mustard At three different ratios 40:40:20 ratio was pressed Adjusted pH-11 by adding Thermostatic water bath [172]
stems, and lentil stalks i.e., 30:50:20, 40:40:20 and further delignified with NaOH at 80 °C for 1 h
and 50:30:20 at boiling peroxyacid at 80 °C for
temperature for 1–4 h 120 min
Natural biomass resources 70:30:0 and boil at hot plate FA/AA was delignified by At pH 11–12 by treating with After pulping and Hot water bath [3]
for 2 h treating with PFA/PAA 14 ml, 35% ­H2O2 solution delignification the spent
mixture at 80 °C for 2 h at 8 °C for 2 h liquor was heated at
105 °C
Dhaincha, corn stalks, rice 90% v/v formic acid conc. FA delignified with PFA at Adjusted pH-11 by adding Thermostatic water bath [173]
straw, wheat straw at boiling temperature for 80 °C required amount of NaOH
120 min at 80 °C for 1 h
Triticale straw (hybrid of rye 20:60:20 or 30:50:20 at – Bleached by PaZEP – – [174]
and wheat) 107 °C sequence, chosen due to
acidic pH of unbleached
pulp

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 Journal of Polymers and the Environment

Fig. 3  A closed loop biorefinery using lignin derived NADESs for biomass pretreatment [134] (With Permission)

Fig. 4  Schematic diagram of

ultrasound-assisted lignin and Rice straw
cellulose extraction technique
Treatment with 2M NaOH (1.0 g rice straw ,20 ml NaOH) for 1.5 hrs at
Washing with 0.1 M NaOH 90 o C at different ultrasonic times(0,10,20,30,40 min.)

Residue Filtrate

Neutralization with HCl to pH 5.5

Washing with water
Concentration at reduced pressure
Precipitation with 3 volumes of 95 % ethanol
Cellulose

Pellet Filtrate
Washing with 70% ethanol and air drying Evaporation of ethanol, concentration
and precipitation of lignin at pH 1.5
Hemicellulose
Solid
Washing with HCl (pH 2.0)

Lignin

with Clostridium beijerinckii DSM 6422, and the butanol • Evaporation method: The components were dissolved in
and ABE concentrations, yields, and productivities obtained water and evaporation carried out in rotatory evaporator
were measured [185]. at 50 °C. The concentrated liquid obtained after
evaporation was put in desiccator for cooling to reach a
Various Methods of Sustainable Synthesis of NADES constant weight [187].
• Stirring and heating method: The two components are
The development of sustainable processes for the combined in a bottle with a stirrer bar and cap and heated
valorisation of lignocellulosic biomass from agricultural, at around 70 to 100 °C in the water bath with agitation
industrial, and forest waste is one of the most evolving until a clear liquid is obtained after 30–90 min reaction
subject concerning extractions employing bio-based solvents [187–191].
and microwave (MW) and ultrasound (US) irradiations • Freeze-drying method: Aqueous solutions of the
[186]. While these new methods are fast and efficient individual counterparts are freeze dried [192].
however additional methods that are simple and easy to use; • Ultrasound-assisted synthesis (UAS): According to
to prepare NADES as mentioned below, Bajkacz [193], the ultrasound-assisted synthesis of

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Journal of Polymers and the Environment

Fig.5  Advantages of NADES
and DESs

Non-volatile

Non-toxic Non-flammable

Thermostable Bio compatible

DESs
NADESs

Biodegradable Low cost

Easy Don't require

preparation purification

NADES is simpler and more efficient than above- temperatures and alkaline concentrations to shorten extrac-
described methods. The component mixture is subjected tion time. The various steps in this method is shown in Fig. 4
to ultrasonic treatment (30Watt power and 37 kHz [197].
frequency) at 50 °C until a homogenous liquid is obtained
(10–15 min) [191, 193]. Advantages of NADES, DES Over Ionic Liquids
• Microwave-assisted synthesis (MAS): when the
component mixture is microwave irradiated for a few Replacing ionic liquids (ILs) and deep eutectic solvents
seconds i.e., 5–30 s at low power i.e., 200W – 800W (DESs), a solvent complying with green standards and har-
[191, 194]. bouring characteristic such as remarkably low cost and eco-
• Grinding method: The components mixture is grinded logically sound emerged as a new class of versatile solvents
with mortar and pestle at room temperature until a that is Natural Deep Eutectic Solvent (NADES). NADESs
homogenous liquid is obtained [190]. represents class of those solvents which is referred and
derived from natural sources [198]. It has tailorable phys-
From all the above environmentally friendly approaches icochemical properties i.e., by changing the form and molar
for NADES synthesis, ultrasound-assisted extraction is sim- ratios of the constituents, they are frequently regarded as
pler method of extracting cellulose and lignin from natural a green. Despite their similarity to ionic liquids, NADES
materials than standard extraction methods [195, 196]. For offers an advantage over ILs due to their lower costs, lower
example, the extraction of cellulose and lignin from Viet- toxicity, and biodegradability. According to [199] the
namese rice straw was investigated utilizing a combina- advantage working with NADES is that they are naturally
tion of ultrasonic irradiation & chemical technique at high abundant and less expensive to be synthesised over exotic
solvents. There are several advantages which are common
between NADES and DESs shown in Fig. 5, that are cost

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 Journal of Polymers and the Environment

Fig. 6   Flowchart of screening of NADES assisted valorisation of orange peel waste followed by biorefinery integrated process

effective as compared to ILs. It can be easily synthesized the components gives NADES its unique features i.e., the
and 100% efficient, extremely perishable as well as bio- physicochemical properties of eutectic mixtures are mostly
compatible green solvent. NADES is non-toxic whereas, determined by the strength of the interaction which is
DES is polemically low toxic particularly Choline Chloride determined by the structure and ratio of the components in
(CC) derived from DES over ILs [142]. The advantages of the combinations (water is frequently added as a component)
NADES and DESs are outlined in schematic diagram pre- [184, 202].
sented in Fig. 6 [142]. One of the advantages of NADES is
the flow behaviour of NADES at room temperature, which is
superior to conventional solvents. They are easier to handle Viscosity
and can be worked in a variety of chemical industries. Aside
from all of the merits, the biggest advantage of adopting Dai et al. [188], studied about physicochemical property
NADES versus DES or even ILs is the ability to prepare of NADES after water dilution with different percentage
NADES at extremely low toxicity levels [199]. of water and was measured at room temperature i.e.,
viscosity of 1,2 -propanediol–choline chloride–water
(PCH) decreased dramatically as water content increased
Properties of Lignin Obtained from NADES Method similar as in the case of glucose-choline chloride-water
(GCH). This shows that the amount of water in NADES
One of the most notable qualities of NADES is their has a significant impact on its viscosity. By adding 25% of
adaptability to individual applications i.e., by varying water to PCH and GCH the viscosity decreased from 33
the NADES constituents and their molar ratios (water is ­ m2 ­s−1 and from 397 to 7.2 m
to 6.1 m ­ m2 ­s−1, respectively,
frequently included as a constituent), their physic-chemical which is close to the range of water i.e., 0.7 ­mm2 ­s−1.
qualities can be modified to satisfy specific process needs Similarly found that viscosity of NADES was achieved
[200]. As a resultant, NADES has been proven to be good to the range of water when small volume of water added
solvents for a variety of enzymatic or chemical reactions, to it, which not only resulted in reduction of viscosity of
pre-treatment of lignocellulosic biomass extracting plant NADES but also changed their shape, allowing them to
components [201]. be used for specific applications [27]. Thus, researchers
To mould the properties of NADES, the relationship have studied extensively ways to overcome high viscosity
between the mixture’s properties and composition must be obstacles by diluting the solvents by adding small amount
understood. The intermolecular hydrogen bonding among of water, which resulted in the substantial decrease in

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Journal of Polymers and the Environment

viscosity and modulates the solvent action [203]. This Vm = M/𝜌 (3)
property is also beneficial in creating NADES that are
suitable for applications. According to [206], the molar ratios of NADES
The physicochemical property i.e., viscosity was also ingredients and molecular properties of HBD (Hydrogen
studied for TCCL3-DES and TCCL3-DES75 (Trehalose Bond Donor) have a major influence on NADES density.
Choline Chloride) were investigated at a temperature Dai et al. studied along with density other properties
range of 20–90 °C. The viscosity of TCCL-DESs was like water activity and polarity are also influenced by water
significantly reduced by adding 25% water, as expected content when NADES was diluted with varying percent-
[204]. The viscosity of undiluted TCCL3-DESs was nearly ages of water [188]. A similar relationship was obtained for
ten times that of the corresponding DESs based on urea GCH (Glucose-Choline-Water), SuCH (Sucrose-Choline
and choline chloride in 2:1 molar ratio [205]. Chloride-Water) and PCH (1,2-propanediol–choline chlo-
ride–water), which showed that there was a linear decrease
Density in density as the water content was increased followed
by a function i.e., y = mx + c where, y = density, x = water
Density is the important characteristic to consider while weight% of GCH, SuCH and PCH, with these calculations,
designing a process [27]. The density of TCCL3-DES and the density of diluted NADES can be computed with a
TCCL3-DES75 was determined at temperatures ranging known amount of water dilution.
from 20 to 90 °C, according to the facts, the density For GCH, with the increase in water content there is
decreases as temperature rises [204]. According to Florindo gradual increase in water activity of NADES followed by
[190], the density at various temperatures was fitted using a function i.e.,
the following equation, which is as follows,
y = 0.354ln(x) − 0.6008 (4)
𝜌 = a + bT (2)
where, y is the water activity, x is water weight % in GCH.
where, ρ ­(gcm−3) denotes density of TCCL-DES or the For the above 50% with water, a linear relationship was
dilution, T (K) is the temperature and a & b are the fitting observed between water content and water activity i.e.,
parameters. The values of a & b were calculated using y = 0.004x + 0.6016 , r2 = 0.99
the linear regression, and the corresponding densities of Research study implies that change in physical properties
TCCL3-DES and TCCL3-DES75 at different temperatures of NADES during dilution may have an impact on their
as shown in Fig. 7 [204]. physicochemical qualities as well as their applications [188].
According to [204], the molar volumes ­(Vm) of TCCL3-
DES and TCCL3-DES75 was also computed using the Polarity
densities and the molar masses using Eq. 3.and the molar
masses decreased in this order TCCL3-DES > TCCL3- Polarity is one of the most essential features of NADES
DES75, indicating that the water has significant impact on in terms of extraction ability and miscibility with other
density. solvents, the majority of NADES reported in the literature
are hydrophilic [191], with hydrophobic NADES being
reported for first time in 2015 [166, 207]. More details are
as follow:
0.24
TCCL3-DES TCCL3-DES75 Hydrophilic NADES -the majority of researchers
reported NADES are hydrophilic or highly hydrophilic
0.22
[208], the polarities ranging from 44.81 kcal ­mol−1 i.e.,
Density (g cm-3)

0.2 higher than water to 51.89 kcal ­mol−1(which is comparable

to methanol), with the ability to be modified by changing
0.18
quantity of water present in the solvent [191]. Because
0.16 of their intrinsic high polarity, hydrophilic NADES have
a high solubilization capability for polar metabolites
0.14 although they could be applied to other non-water-soluble
metabolites [208].
0.12
290 310 330 350 370 Hydrophobic NADES—when compared to hydrophilic
Temperature (K) NADES, according to Ribeiro et al. hydrophobic NADES
were shown to have lower viscosity due to the elimination
Fig.7  Relationship curve between Density ­(gcm−3) versus Tempera- of coulombic charge interactions [207]. NADES has a wide
ture (K)

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 Journal of Polymers and the Environment

Table 8  Conductivity of Compositions or Molar ratios Abbreviations Molar ratios Conductivity

NADES at normal temperature (mS ­cm−1)

Fructose: glucose: sucrose: water FGSH 1:1:1:11 0.0012

Fructose: choline chloride: water FCH 2:05:05 3.1
Glucose: choline chloride: water GCH 2:05:05 6.81
Glycerol: choline chloride: water GlyCH 2:01:01 13.78
Lactic acid: choline chloride: water LC 1:01 6.76
Lactic acid: glucose: water LGH 5:01:03 0.114
Methanol – – 0.00424
Malic acid: b-alanine: water MAH 1:01:03 0.551
Malic acid: choline chloride: water MCH 1:01:02 5.91
1,2-Propanediol: choline chloride: water PCH 1:01:01 12.09
Proline: malic acid: water PMH 1:01:03 1.06
Sorbitol: choline chloride: water SoCH 2:05:06 6.77
Sucrose: choline chloride: water SuCH 1:04:04 3.39
Water – – 0.00208
Xylose: choline chloride: water XCH 1:02:02 3.15
Xylitol: choline chloride: water XoCH 1:02:03 13.55

range of polarity, ranging from more polarity than water to (non-polar) > base-organic acid ≈ base-sugar > base-polyal-
a polarity close to methanol. According to Dai et al., water cohol. In addition, NADES with low and high conductivity
addition has a significant impact on the polarity of NADES, such as PMH LGH SuCH, GCH and PCH were chosen to
culminating a polarity identical to itself. Therefore, all these study how water affects conductivity. It was studied that the
evidences suggest that by adding water, the physical features conductivity of few NADES diluted with varying amount of
of NADES can be modified in a regulated manner [208]. water, and it was found that conductivity initially increased
Sharma, S. et al. [27], discussed polarity of NADES with increasing water quantity, then dropped after reaching
is an important feature since it impacts their solubilising a peak value approximately 10–100 times higher than that of
capability. NADES derived from organic acids are reported 100% pure NADES. In addition, it was also seen that maxi-
to be most polar i.e., ~ 45 kcal/mol, following that NADES mum conductivity diluted with 60% water in GCH, PCH,
derived from sugars and amino acids; whereas NADES SuCH and PMH whereas, LGH had the highest conductiv-
derived from sugars and polyalcohol’s have the least ity diluted with 80% water. Therefore, the conductivity of
polarity, nearly equalling that of methanol i.e., ~ 52 kcal/ NADES increases because of lowered viscosity by dilut-
mol. Polarity of NADES has significant impact by adding ing with a certain amount of water, and the conductivity of
water. For example, notable change in the structure NADES may be customized by adjusting the water quantity.
of Pro-CC-H and LA-Glu-H was seen when 50% (v/v) As a resultant, NADES with amino acid or organic acid has
water changed the polarity of 1,2-propanediol-CC-water low conductivity whereas, NADES with choline chloride has
(Pro-CC- H) and lactic acid–glucose-water (LA-Glu-H). a high conductivity. According to Dai et al. [208], NADES
According to Dai et al. [187], structural change could be composed of polyalcohol and a base such as PCH are more
caused by the breakdown of hydrogen bonds between the conductive than those composed of a sugar and a base such
components, such as, Urea-CC and glycerol-CC which as SuCH, which could be attributed to PCH’s substantially
shows comparable results. lower viscosity. Lastly, the conductivity of most highly vis-
cous NADES, particularly those containing sugar or amino
Conductivity acid i.e., 300–600 m ­ m2 ­s−1, have a poor conductivity i.e.,
lower than 10.
The conductivity of few normal NADES and diluted NADES Rengstl, et al. discussed temperature-dependent specific
was measured at room temperature as shown in Table 8. conductivity (k) of NADES reagent using custom-designed
According to Table 8 [188], GlyCH had the highest equipment between temperatures ranging 25–85 °C as
conductivity whereas, FGSH had the lowest value of con- well as dielectric relaxation spectroscopy [209, 210].
ductivity, which was comparable to water and methanol. According to Craveiro et al. [209], found that amino acids
NADES conductivity increases in the following order: with high polar organic acid-based NADES have greater
sugar-sugar > organic acid-sugar > organic acid-amino acid conductivity than NADES derived from amino acids and

13
Journal of Polymers and the Environment

Fig. 8  Lignin commercial brands and their applications by the prominent companies [256]

sugars. Kumar et al. [135] studied the conductivity of acidic efficiency. According to [211], may be due to the weak
and neutral choline chloride-based NADES solutions. The chemical reaction based on insufficient solvent supply to
conductivity of diols as HBD was somewhat higher than adequately engross the biomass solid sample. However,
that of dicarboxylic acids [27]. Therefore, NADESs have higher the value of the solid-to-solvent ratio, more problems
been shown to be efficient solvents for a variety of chemical arise during solvent dispersion in the sample, further
and enzymatic reactions and for extracting plant-derived reducing extraction efficiency.
components and pre-treating lignocellulosic materials [184]. According to literature [212, 213], natural deep eutectic
solvent [(citric acid: glucose: water; 1:1:3): water solution
(1:9 w/w)] provides highest removal yield while extracting
Factors Influencing the Extraction Process pectin from Myrciariacauliflora, in another example the
Using Deep Eutectic Solvents greatest yield of pectin from pomelo peels was obtained
using 5:2:5 (Choline chloride: glucose: water) NADES.
There are several processing parameters, such as the solid-
to-liquid ratio, temperature, time, pH, and solubility, etc. (b) Effect of time
which plays important roles in the extraction of diverse
bioactive components utilizing greener solvents. We will According to Skarpalezos, D. et al [214], during the
discuss some major factors affecting the efficiency of various extraction methods, the operation variable of
extraction process using DES. extraction time plays a crucial role. Longer extraction
time raise expenses, whereas, shorter extraction time
(a) Effect of solid-to-solvent ratio risks leaving significant amounts of target compounds in
the sample, rendering the method in efficient. However, it
The solid-to-solvent ratio plays an important role in has been observed that the type of extraction determines
keeping the reaction system homogenous throughout the the extraction time required such as heating, ultrasound or
extraction process with deep eutectic solvents. The reaction microwave energy-assisted methods requires more energy
system is not observed to be homogenous at lower values to conduct. Therefore, the usage of DES has resulted in
of solid-to-solvent ratio due to presence of a little quantity significantly short extraction times for all extraction methods
of DES chemical that was observed to reduce the reaction used.

13
 Journal of Polymers and the Environment

(c) Effect of temperature polarities and their molecular interactions with the
products. According to [208], DES solubilizing ability
It is well known that temperature plays a key role in the can be increased by varying the percentage of water used
process of extracting bioactive components using DES and depending on the target chemicals. For e.g.; rutin was more
NADES. It is expected that the extractions temperature will soluble in Choline chloride: glucose with 5% water content
have an impact on both the time it takes and how effectively but, carthamin was found to be more soluble in same DES
it works. An increase in temperature results in a decrease in with 10% water level.
viscosity, which leads to greater extraction results. However,
this rise in temperature needs to be considered because it
could affect the thermolabile molecules [214, 215]. An Processing of Lignin for Production
increase in DES reaction temperature resulted resulted in an of Value–Added Products
increase in lignin removal. Lignin elimination was enhanced
by approximately 7.57% when the DES reaction temperature The idea of biorefinery was first derived from refinery
was raised from 100 to 120 °C at 180 min DES reaction of petroleum, in which various methods were used to
time for 40 mins. Since higher DES reaction temperature manufacture numerous fuels and chemicals from crude
reduces surface tension and viscosity while increasing the petroleum [222]. The biorefinery approach integrates
DES diffusivity by causing hydrogen bonds between its hybrid technologies from several sectors such as agriculture,
components to break [216]. Moreover, higher temperature engineering, microbiology, and chemistry. Furthermore,
enhanced the ability of DES to cleave many chemical bonds biomass can be converted into high value-added products
between lignin, cellulose, and xylan thus led to enhanced (e.g., biofuels energy and chemicals) from its constituents
delignification [217]. Due to presence of side reactions, [223].
high temperatures and longer times contribute to poor Biorefinery processing paths must be carefully
delignification [218]. Also DES pretreatment was conducted designed. Various technological processes, including as
at 60 °C for delignification of watermelon rind [211]. mechanical, chemo-mechanical, chemical, biochemical
processes and thermo-chemical are typically used in
(d) Effect of pH tandem to transform feedstock into a variety of value-
added products in an integrated biorefinery process
NADES pH is regarded as one of the most important [222]. The production of biofuels like biodiesel,
elements determining extraction efficiency since it has ethanol, methane, bio-oil etc. from crop plant residues,
a considerable influence on the molecular interactions micro- and macroalgae, and other biomass wastes using
between the eutectic solvent and the target solutes [219]. thermos-bio-chemical processes has been found to be an
According to [220], has the potential to affect the charge of environmentally friendly method for generating energy
the bioactives being extracted, as well as their extraction [224]. To better demonstrate the biorefinery methods,
efficacy. The pH values of several deep eutectic solvents many instances of converting plant-derived or agricultural
vary with temperature, and their acidity is generally wastes to value-added products are presented, along with
controlled by the nature of the hydrogen bond donor inputs, and outputs as depicted in Table 9 [222].
[221]. NADES acidic nature breaks a greater number For production of lignin as value added product, lignin
of bonds, resulting in a faster extraction procedure. processing should be carried out from different sources.
Glucose: glycerol and glucose: ethylene glycol these two Lignin instead of energy generation should be used as
NADES ratio have shown the greatest potential for protein feedstock for value added product [233]. Henceforth,
extraction during orange peel waste valorisation, because different sources of lignin can be modified into other value-
it is nearly in the range of neutral pH [184]. However, added product such as vanillin, carbon fibres, polyurethanes
based on the pH value of residual orange peel, it can be and nanomaterials etc. for several applications ranging
further used as fertiliser as well as utilised in the biogas from biomedicine to automobile industry. Additionally,
generation process [184]. Highly polar compounds require biorefineries viability increases when value added products
an acidic solution to boost extraction efficiency. As a are obtained [234].
result, several NADES or DES based on organic acids are Every year the agricultural food business generates huge
frequently the best option [220]. tonnes of lignocellulosic residue, one of the example is Musa
acuminate var. Dwarf Cavenish (banana leaves), due to its
(e) Effect of solubility composition and its ability to produce high lignin content
from leftovers to value added products which is to be valor-
The key characteristic of DES and NADES is their ised, and with the economic cycle in mind, this valuation is
solubility, which is connected to the similarity of their becoming increasingly required and critical, providing value

13
Journal of Polymers and the Environment

Table 9  Conversion of various plant-derived wastes in value-added products

Crop Input Output References

Cassava peels S. cerevisiae, Cassava peels, NaOH, enzymes, Methane Ethanol, [225]
manure inoculum, water and electricity
Citrus waste S. cerevisiae, Citrus waste, water, Sulfuric acid, Biogas, pectin, ethanol, D-limonene [226]
heat, electricity, steam, nutrients, and ethanol
Corn distillers dried air grains Corn distillers air dried grains, H
­ 2SO4, water, Xylose rich stream and arabinose-rich stream [227]
heat, and electricity
Grape pomace Grape pomace, NaOH, C ­ O2gas, water, ethanol, Polyphenols, volatile fatty acids, polyhydroxy [228]
­N2, acidogenic microbial consortium, alkanoates, methane
methanogenic microbial consortium, glucose
nutrients, Cupriavidus nectar, and electricity
Olive mill waste Olive mill waste, ­N2, ethanol, water, air, heat Fuels, biochar, polyphenols, mono/poly- [229]
and electricity unsaturated fatty acids,
Rapeseed straw, cake, glycerol Rapeseed straw, cake, and glycerol NaOH, H ­ 2O2, Methane, Ethanol, ­H2 -
sodium citrate buffer, water, nitrogen, digested
manure, enzyme, steam and electricity
Rice husk and Arundo donax A.donax, Rice husk, NaOH, HCl, ethanol, acetic Cellulose nanocrystals, lignin hemi-cellulose A, [230]
acid, ­H2SO4, ­H2O2, water and electricity hemi-cellulose B, silica,
Tomato seeds and peels Tomato seeds and peels, C ­ O2, NaOH, water, ­N2, Oils, carotenoids, proteins, cellulose, sugars, [231]
and electricity lignin
Wheat straw S.cerevisiae, wheat straw, enzyme, ­N2, digested Biogas, Bioethanol, Biohydrogen, [232]
manure, acetate buffer, nutrients, water and
electricity

to banana leaf residue by using it as a raw material in manu- cellulose and chitosan show significant promise in several
facturing of lignocellulosic micro/nanofibers (LCMNF) and applications and the results are very encouraging which can
to examine its potential application in paper making [235]. boost the effectiveness and productivity of several industries,
Another value-added product of cellulose and chitosan including agriculture [243].
is chitosan-cellulose composites, which can be prepared
by three different methods i.e.; chemical, physical, and
biological [236]. According to Wu et al. [237], a thin
film was made by combining chitosan and cellulose with Applications of Lignin Derived by Green
trichloroacetic acid, and the resultant chitosan/cellulose Synthesis
blend showed antibacterial activity against E. coli and S.
aureus when utilized as wound dressing material. Green solvents are biodegradable, recyclable, non-volatile,
Chemically produced cellulose-chitosan composite has non-toxic, and low-cost preferably manufactured from
great film-forming capacity, is biodegradable, and has widely available resources [244]. Green solvent-based
minimal toxicity. Comparing to chemical method process, research is being readily acceptable; therefore, principles
physical method is expensive. However, the purity of the should be considered when designing green solvents
composites produced by physical procedure is higher than to replace conventional solvents. According to [245],
that produced by chemical procedure [238, 239], also employing lignin as a macromolecule to create value-added
membrane stability is poorer than that achieved by chemical products to synthesize innovative, efficient, and reactive
process, resulted in decrease in tensile strength. For ex. macro-monomers, the structure of lignin is altered by
Fabrication of nanohydroxyapatite/chitosan/carboxymethyl changing the nature of the chemical sites or increasing the
cellulose porous composite bracket [240]. reactivity of the hydroxyl groups.
According to [241], biologically produced cellulose/ Natural fibres such as cellulose used as a reinforcing
chitosan composites, such as film and fibre, shows remark- agent in bio-composites, whereas lignin can also use as
able mechanical properties, anti-bacterial capabilities, water a functional filler and polymer compatibilizer. Some of
retention, and other benefits, implying large potential in the the lignin-related research for example, has included the
biomedical sector, and different moulding techniques used to invention of a flocculent for dye removal, composites with
create membrane or scaffold structure prepared using bacte- improved fire behaviour, film fabrication, and polyelectrolyte
rial cellulose, is a new type of cellulose/chitosan was formed membrane [246–250]. Studies mentioned discussed earlier
successfully [242]. Therefore, composite materials made of such as flocculent for dye, composites, etc.; used lignin with

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no prior surface modification, whereas other researchers of blending effect to allow large scale application in
used grafting processes to improve surface characteristics separation, purification of biochemical products, and
[234]. other important processes in industrial application.
The other applications for lignin as a macromolecule Without proper utilization of treatment, agro-waste
include lignin-modified phenol–formaldehyde resins. A can create negative challenges affecting sustainability
phenolation procedure is carried out on lignin prior to the for society and industries. Thereby knowledge of the
manufacture of the phenol–formaldehyde resins [251]. chemical as well as the physical composition of agro-
According to [252], lignin can be employed directly in the waste is important to find the suitable technological
manufacture of phenol–formaldehyde resins without prior treatment which depends on the economic and local
phenolation. situations. More scientific efforts are expected to
minimize the costs for industries that use agro-wastes
as feedstock; because the huge amount of agro-wastes
Challenges to Current State‑of‑the Art particularly from the agriculture sector can be utilized
Technologies and Future Perspectives as feedstock; nonetheless collecting them from where
they are being generated is a challenging task. Recycling
Resource declination and population growth have and material recovery must be effectively introduced and
opened the eyes towards utilization of agriculture sector implemented to produce economic benefits. Continuous
productivity into potential advantageous products since research on lignin materials is critical for environmental
technological advancement has increased farm produce protection, resource conservation, and green and
which in turn provides huge agro-waste. Since the impact sustainable development. In conclusion, successful
of agro-wastes on the environment is inevitable causing waste management and treatment would help to realize
biodiversity loss as well as pollution originator which the concept of sustainable development for the sake of a
can be promoted to sustainability by converting agro- better nation and global community.
wastes into potential advantageous products for example
lignocellulosic biomass obtained from agro-waste is
considered as most potential material which can be Current Market
utilized in the future development of useful products.
Future research perspectives are as follows: new The largest worldwide source of lignin feedstock is kraft
technology should be used in extracting smaller pulping, but this is presently less important commercially
molecules from the complex structure of lignin and than sulfite pulping because of the realistic applications of
through a certain measure of art technology smaller lignosulfonates, whereas almost all kraft lignin is burned
molecules can be combined with other materials to form for power generation and heating. However, kraft lignin
a manageable compound. E.g.; ionic liquids (ILs) and has emerging applications because of the size of global
Deep eutectic solvents (DES) present obstacles in the production.
use of green solvents, and NADES performs better than Kraft lignin is valorized by corporations including West
the other solvents for lignin extraction which has various Fraser, Ingevity, RISE Ligno Demo AB, Domtar, Suzano,
advantages. The challenges pertaining to the use of ILs Liquid Lignin, and West Rock, while those producing
are highly expensive, decompose at high temperatures lignosulfonates include Rayonier Advanced Materials,
(have limited thermal stability), toxic which makes Borregaard, Domsjo Fabriker AB, Nippon Papers,
them unsuitable for certain applications also the main and Sappi Biotech GmbH as shown in in Fig. 8. The
challenge of ILs and DES particularly their toxicity and combined annual commercial-scale output of lignin and
environmental hazards, could be solved using NADESs. lignin-derivatives by these companies is 1.8 million tons.
Therefore, NADES is a more efficient extraction process Four-fifths of the lignin market, excluding combustion, is
with less energy usage and shorter reaction time and supplied by lignosulfonates, while kraft contributes 16%
produces higher extraction yields and is considered and the other 5% is made up of organosolv and hydrolysis
environmentally friendly, and can be tailored to lignin lignins [253].
extraction applications. Secondly, more research should Bor regaard of Nor way is t he major global
be done to improve the compatibility of lignin with lignosulfonate producer, trading on four continents and
other materials by producing a dispersion of lignin claiming to deliver sustainable lignin-based materials
macromolecules in the matrix. Thirdly, the industrial including battery components, ceramic materials, binding
preparation process should be organized in a way to reduce agents for animal feed, briquetting, textile dyes, pesticides,
cost and pollution. Lastly, selective separation of lignin and dispersing agents for concrete [254].
research should be carried out to break the limitation

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Journal of Polymers and the Environment

The next most prominent producer, of approximately thereby assigning functional unit to lignin and main
120,000 tons of powder lignin annually in its biorefinery product separately can easily understand how lignin
facility, is Domsjö Fabriker of Sweden. Its main external is considered in biorefinery may help in the reduction
markets are for concrete and feed industry additives, agri- of formation of bio-product residues. All the data for
culture, and roadbuilding. The parent group, Aditya Birla, biorefineries is collected from lab and processing models;
comprises 50 companies in almost 40 countries, operating considering this research gap it is important to gather
130 production units [255]. primary data to produce lignin from the real large-scale
Notwithstanding the abovementioned varied list of source which is missing from the public domain should
products, and although only cellulose is a more widely be considered. On the contrary, climate change depletion
available biopolymer, lignin remains significantly under- threats concurrent to biorefinery is the use of non-
used and its valorisation is at an early stage. Nevertheless, conventional green solvents therefore NADES offers an
a number of mature companies have proved that it can be a economic and low toxic profile. Until recently there is
very valuable and innovative biorefinery resource to make no other solvent that could be effectively used and is the
high-performance, sustainable biofuels, biomaterials, and ideal solvent for various industrial waste usage. Beyond
biobased chemicals. this, biomass pre-treatment depends on composition
conditions which particularly have merits and demerits
and can have a substantial effect on the holistic climate
impact. Nonetheless, the rising understandings of the
Conclusion significance of NADES and their use suggest that it has
the potential to impact future searches in various fields
Growing interest to reduce hazardous compounds such as chemistry, biology, and biomedical applications.
envisaged the term ‘’green’’ gaining new meaning in
chemistry i.e., green chemistry for a sustainable approach
Author Contribution AM: Conceptualization, Methodology,
to eliminate hazardous synthesis. Since manufacturing Investigation, Formal analysis, Writing—Original Draft, Writing—
industries involve hazardous synthesis that need to be Review & Editing. SPS: Investigation, Writing—Original Draft,
addressed and replaced by a new generation solvents. Writing—Review & Editing. MJ: Supervision, Conceptualization,
Therefore, researchers are turning towards a natural and Writing—Review & Editing, Validation, Resources, Funding. MMN:
Supervision, Conceptualization, Writing—Review & Editing. TSA:
biodegradable synthesis that can prevent the threat of Validation, Writing—Review & Editing. NA: Conceptualization,
unsafe and toxic synthesis. Henceforth, lignin isolation Writing—Review & Editing.
from agricultural wastes is an effective blueprint which is
considered in a few points below- Funding We are thankful to the Universiti Putra Malaysia for funding
this work under Putra Grant-GP-IPS/2021/9698100.
The use of green solvents not only increases yield but
also reduces energy consumption ultimately decreasing Declarations
production costs, protecting human and environmental
health in the short and long terms. One such example Conflict of interest The authors herewith declare that there is no con-
includes for future applications which are now in their flict of interests regarding the publication of this research article.
budding stage is NADES. NADES usage for pre-treatment
techniques to extract lignin from agro-waste is attract
global recognition because of its non-hazardous nature.
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