Industrial Crops & Products 115 (2018) 330–339

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Industrial Crops & Products

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Extraction and isolation methods for lignin separation from sugarcane T

bagasse: A review
Saleh Al Arni
Chemical Engineering Department, College of Engineering, University of Hai’l, Hai’l 81451, Saudi Arabia

A R T I C L E I N F O A B S T R A C T

Keywords: This paper intends to review different extraction and isolation methods recently explored for lignin separation
Lignin of sugarcane bagasse from sugarcane (Saccharum officinarum L.) bagasse. Initial bagasse processing is a pre-treatment mechanical
Sugarcane bagasse action (milling) that facilitates applying further conversion technologies. There are several methods that have
Ionic liquid methods been developed for the extraction and isolation of the solubilized lignin from sugarcane bagasse; these include
Alkaline pulping methods
alkaline and ionic liquid methods. The insoluble lignin can be separated by the treatment of concentrated sul-
Alkaline dioxane extraction methods
furic acid. The quantity of sugarcane lignin fraction depends on the techniques applied and the aim of studies,
but it has a range of 17–32% of biomass while the average value is about 23% of biomass. This fraction value has
a major content in non-wood biomass and it is rich with aromatic chemical compounds.

1. Introduction is used to cultivate edible mushrooms, such as shiitake (Lentinula edodes

(Berk.)) (Arni and Converti, 2012), also it is used as fertilizers
The lignin (lignum) means wood and it is a component of lig- (Espinoza-Acosta et al., 2014). The sugarcane bagasse is used in in-
nocellulose which consists also of cellulose and hemicellulose. This dustry to produce power as a fuel to generate electricity (Deepchand,
material is a natural complex biopolymer structure of carbohydrates. 2005), to make paper (Poopak and Reza, 2012), in building materials
An increased interest has been noted recently in the extraction of (Loh et al., 2013) and feedstock to different products based on fer-
lignin from non-wood biomass such as, sugarcane, wheat (Triticum aes- mentation for the production of bio-based materials (Carvalho et al.,
tivum) straw, bamboo (Bambusa vulgaris), alfalfa (Medicago sativa), kenaf 2002a,b; Carvalho et al., 2004; Carvalho et al., 2005; Converti et al.,
(Hibiscus cannabinus) and flax (Linum usitatissimum) fiber (Rı́o et al., 2003; Santos et al., 2003; Santos et al., 2005a,b; Moldes et al., 2006;
2004; Ververis et al., 2004; Zhang et al., 2013). The focus of this paper is Sarrouh et al., 2007; Cunha et al., 2006,2009; Capecchia et al., 2015).
concentrated only on the sugarcane bagasse as biomass raw material of Bagasse also used as biosorbents for the removal of heavy metals ions
lignin source. This waste fiber is considered as the amount of remaining such as Cd, Cu, Pb, Zn, Ni and Cr (VI) ions (Junior et al., 2006), also for
material after milling in sugar manufacturing or as residues in-land after oil absorbing in the absence of water (Said et al., 2009). The summary
harvests. It consists of two types of herbaceous plant fibers: rind and of usage of bagasse is presented in Fig. 1.
pith, which are longer than hardwood fibers and shorter than softwood The main focus of the present paper is the delignification processes
fibers (Arni and Converti, 2012). All factories that are producing sugar that employed in the treatment of sugarcane bagasse to extract and
from sugarcane have amount residues of this waste fiber, and typically isolate lignin fraction.
produced about 30% of bagasse. It contains about 10–15% sucrose and
12–16% fiber (Arni and Converti, 2012). This biomaterial has a certain 2. Processes for decomposition of lignocellulosic materials
value, especially because of its sustainable and its economic interest for
production fine chemical from renewable resource. Technologies used for bagasse decomposition are the same used in
Today, there are a lot of bagasse applications; a search in literature agricultural waste biomass decomposition. Usually, the decomposition
data shows a number of studies have been done on sugarcane bagasse processes depend on the ending goal of treatment, biomass type and
use and its application (Sene et al., 2001; Arni, 2004a,b; Zilli et al., quantity. Many researchers have established various processing tech-
2004; Junior et al., 2006; Doherty et al., 2007; Boussarsar et al., 2009; niques that can be used to convert these materials into various new
Griffin, 2011; Cunha et al., 2011; Rocha et al., 2015a,b; Wahba et al., products (Sun et al., 2000; Lavarack et al., 2002; Ou et al., 2009;
2015; Costa et al., 2017). There are different levels for the reuse of Laopaiboon et al., 2010; Li and Ge, 2011; Rocha et al., 2011, 2012,
bagasse as a raw material starting from domestic to commercial use. It 2015a).

E-mail address: [email protected].

https://doi.org/10.1016/j.indcrop.2018.02.012
Received 29 May 2017; Received in revised form 2 February 2018; Accepted 4 February 2018
0926-6690/ © 2018 Published by Elsevier B.V.
S.A. Arni Industrial Crops & Products 115 (2018) 330–339

Fig. 1. Schematic diagram of processing and potential uses of bagasse.

There are two general categories of technologies for conversion of The steam explosion is a physical pretreatment method that is used
bagasse, firstly, the processing for conversion into energy products and for cellulosic materials pretreatment to the solubilization and separa-
secondly, processing for conversion into non energy products. Fig. 1 tion of one or more of the four major components of biomass (hemi-
gives a general overview of processes and potential uses of sugarcane cellulose, cellulose, lignin, and extractives). During this process, steam
bagasse. permeates the biomass material and initiates a chemical autohydrolysis
Processing of energy products aims to produce power in its different reaction, because some organic acids that are presented in biomass can
forms, such as, heat and steam, electricity, synthetic fuel oil, charcoal, be catalyzed and help remove of the hemicellulose and lignin from their
producer gas, methane, ethanol, methanol and bio-diesel. The main biomass structure (Pol et al., 2015). This phenomenon is observed
conversion processes to energy products are thermochemical processes, during the steam processes, such as the formation of acetyl groups
such as, combustion, pyrolysis, and gasification. The most frequent (Rocha et al., 2015a,b). Sometimes, chemicals, such as sulfuric acid, can
using of sugarcane bagasse for energy production is the direct com- be added to improve efficiency of the process (Rocha et al., 2015b). On
bustion (process based on solid-state) which consumed on-site the other hand, the most common chemical pretreatment methods
(Mullinger and Jenkins, 2008; Arni et al., 2010c). make use of dilute acid, alkaline, organic solvent, ammonia, sulphur
The biological processes to convert bagasse into energy are based on dioxide, carbon dioxide or other chemicals to make the biomass more
fermentation processes to produce ethanol, and Anaerobic Digestion adequate for further applications (Motaung and Anandjiwala, 2015).
(AD) to produce biogas (Converti and Del Borghi, 1996; Converti, 1998; Rocha et al. (2015a), in their investigation of 60 sugarcane samples,
Converti et al., 1998, 1999). Saxena et al. (2009) presented a review presented ratios of mass fractions of lignin extracted from sugarcane
article on various biochemical processes for conversion of biomass into bagasse which are determined by pretreatment of concentration sul-
biological hydrogen gas and ethanol. furic acid method. These ratios are 7.4/1 (total lignin/soluble lignin),
Biological pretreatment is sometimes used in combination with 1.2/1 (total lignin/insoluble lignin) and 0.2/1 (soluble lignin/insoluble
chemical treatment to solubilize lignin in order to make cellulose more lignin). This means that the extraction of lignin need successive treat-
accessible to hydrolysis and fermentation. Different microorganisms are ment, because the major of lignin is insoluble. On the other hand, the
able to partially or completely degrade biomass which is described acid method is not adequate to treat lignin, but it can treat hemi-
elsewhere (Pandey et al., 2000). In addition, for lignin depolymeriza- cellulose effectively (Lavarack et al., 2002; Fogel et al., 2005; Geddes
tion can be performed by fungal as bio-catalytic to lignin degradation. et al., 2010; Rocha et al., 2011).
This process can be also done by certain bacteria or consortia bacteria The alkaline hydrolysis process is a breakdown of the intermolecular
(Cho et al., 2004). Jääskeläinen et al. (2003) found a high yield (83%) ester bonds cross-linking with lignin and other material components as
of lignin by enzymatic hydrolysis. celluloses and hemicelluloses. It is more effective to solubilize a greater
On the other hand, there are a variety of methods that can be used fraction of lignin (Mosier et al., 2005; Rocha et al., 2012). Rocha et al.
to convert bagasse into non energy products, such as physical methods, (2012) demonstrated that the steam explosion and alkaline delignifica-
chemical methods, mechanical extraction methods and biological tion processes are good for extraction of lignin from bagasse.
methods. The selection of the adequate process of treatment depends on
the final goal of treatment. 3. Extraction and isolation of lignin from sugarcane bagasse
The physical and chemical pretreatment methods may be used to
break down biomass components. The physical pretreatment refers to Establishing and selecting a method for isolation and recovery of
reduce the size of raw material by mechanical actions to make it ac- lignin from non-wood biomass such as bagasse is not an easy task.
cessible into successive treatment such as biological and/or chemical However, there are several methods that are recently developed to
treatment. extract and isolate the lignin from sugarcane bagasse, such as alkaline
The major techniques employed to break down biomass components method (Li and Ge, 2011; Moubarik et al., 2013; Wahba et al., 2015),
are based on the hydrolysis method. This method, which is sometimes and ionic liquid (Tan and MacFarlane, 2009; Tan et al., 2009).
called saccharification, that is used to break down the hydrogen bonds
in the lignocellulosic biomass fractions by removal of the surrounding 3.1. Alkaline methods
hemicellulose and/or lignin along with modification of the cellulose
microfibril structure and recovering the resulting soluble monomeric In this section, a briefing of some extraction and isolation of solu-
and/or oligomeric sugars (Motaung and Anandjiwala, 2015; Rocha bilized lignin from sugarcane bagasse methods, is presented (Wahba
et al., 2015b). et al., 2015; Moubarik et al., 2013).

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3.1.1. Alkaline pulping methods a) First step, the bagasse is washed with hot water at 80 °C, then it is
The delignification method is based on the treatment by soda so- dried for 4 days at 40 °C in a circulating air oven until 10% w/w
lution (alkaline delignification), usually after pre-treatment by me- moisture content is obtained, and then it is milled;
chanical and hot water, at about 100 °C for about one hour or more, b) The milled powder was immersed in aqueous solution, 0.5 mol L−1
with different concentrations of soda and biomass (solid) to liquid ratio; NaOH (1:10 m/v) with ratio 1:10 g/mL, then autoclaved for 1 h at
briefly: 120 °C and then filtered. The pH of filtrated (black liquor) was ad-
justed to 5.5, with 1.0 mol L−1 of HCl, and then concentrated to
3.1.1.1. First step (Pre-treatment). Sugarcane bagasse was air-dried at obtain a small volume (reduced);
ambient temperature for three days until humidity reach to 8–10%, c) Adding three volumes of 95% ethanol (v/v) to the resulting liquor
then cut into small pieces (1–2 cm), grounded and screened to pass a for precipitation hemicellulose and silicon compounds. After this,
through 1.0 mm size screen. The dry powder is treated with hot water at the ethanol present in the resulting liquor is removed and the pH is
70–80 °C for 2 h with solid-to-liquid ratio 1:10 w/w, and then it is lowered to 1.5 for precipitation of lignin, the lignin obtained was
cooled to 25 °C, washed with water at the same above mentioned ratio filtered, washed, and dried (lignin obtained with this step is so
and centrifuged for 10 min at 2000 rpm to separate the solubilized called Lig-Alk).
hemicelluloses. d) The second type of lignin was obtained from the black liquor
(200 mL) and used directly in the oxidation process by adding 14%
H2O2 (w/v) to reflux at pH 13, for 2 h at 98 °C, then purified and
3.1.1.2. Second step (Pulping method). The separated solid was pulped precipitated as described above (lignin obtained with this step is so
at 90–98 °C by sodium hydroxide solution (15% NaOH m/v) with solid called Lig-Ox).
to liquid ratio 1:10–1:18 w/w at 90 °C for 1.5–4 h, under constant e) Other type of lignin was obtained through the acetylation of Lig-Alk
stirring, then filtered to obtain the black liquor without any fibrous by dissolving 1.0 g of Lig-Alk in 10.0 mL of anhydrous pyridine and
materials. The filtrated (black liquor) was acidified by sulfuric acid (5N 20.0 mL of anhydrous acetic anhydride under an inert atmosphere
H2SO4) to pH 2, in order to precipitate the acidified lignin then washed and agitated at 28 °C for 2 days, then added 20.0 mL of di-
by water and collected by centrifugation and air dried, schematically chloromethane/MeOH solution (1:1 v/v). The resulting solution
illustrated in Fig. 2 (Wahba et al., 2015; Moubarik et al., 2013). separated with 2.0 molL−1 of HCl until pyridine had been com-
The yield of lignin obtained from this method was 13%. The two pletely removed, then washed with 10.0 mL of water and dried
sequential stages of treatment enabled to isolate 86% of original lignin (lignin obtained with this step is called Lig-Ac).
from sugarcane bagasse.
The total yield of precipitated lignin from this method according to
3.1.2. Other similar methods sugarcane bagasse weight are: Lig-Alk: 7.2%; Lig-Ox: 5.5%; and Lig-Ac:
3.1.2.1. Soda-pulping method. Costa et al. (2017) used the lignin 6.2%.
extracted from sugarcane bagasse for assembling micro-particles. The
extraction and modification of lignin derivative from sugarcane bagasse 3.1.3. Extraction by dioxane and hydrochloric acid and by alkali solution
done by soda-pulping process to solubilize the lignin present in Hoareau et al. (2004), studied the bagasse lignin that pretreated by
biomass, as following: cyclohexane-ethanol. The methods of extraction and modification of
lignin from sugarcane bagasse are as following:

3.1.3.1. Pretreatment. The extraction of sugarcane bagasse was done in

Soxhlet for 2 days with a mixture of cyclohexane-ethanol (1:1, v:v) then
with water for one day and dried until constant weight in an air-
circulated stove at 60 °C, then grounded to obtain a powder (1 mm
diameter).

3.1.3.2. Treatment by dioxane and hydrochloric acid. The dry powder

treated with a dioxane solution and 0.1 N aqueous hydrochloric acid
(8.5:1.5, v:v) with ratio (100 g/1L) and heated under nitrogen at 100 °C
for 2 h, then filtered and washed three times with a fresh dioxane-water
solution (3 × 500 mL, 8.5:1.5) without hydrochloric acid. The filtrates
concentrated by evaporation under vacuum to eliminate dioxane in
conditions that maintain the pH solution above 1 to avoid excessive
depolymerisation of lignin, then centrifuged and the precipitation dried
under vacuum (30 mbar) over phosphorous anhydride as purity of
bagasse lignin. The purity of bagasse lignin is 90% related to soluble
lignin and the yield of acidolysis lignins isolated from bagasse is
estimated about 10% of fiber treated. (Hoareau et al., 2004).

3.1.3.3. Treatment by alkali (KOH) solution. Sugarcane bagasse (dry

powder) stirred with a 0.5 M aqueous KOH solution with ratio 50 g/
1.5L under nitrogen at 35 °C for 3.5 h, then filtered and washed with
water then with ethanol. The filtrate is neutralized with a 6 M acetic
acid solution to pH 5.5.
This filtrate is treated by three volumes of 95% ethanol for pre-
cipitation of hemicellulose fraction (hemicellulose isolation). Then after
evaporation of ethanol, the concentrated filtrate is precipitated in water
Fig. 2. Illustration method of extraction and isolation of lignin from sugar cane bagasse and adjusted with a 6 M HCl solution to pH 1.5 to obtain alkali lignin
(adapted from Moubarik et al., 2013).
(lignin isolation). Then centrifuged and washed with acidified water to

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pH 2.0 and then dried under vacuum over phosphorous anhydride. The 4) 0.5 M NaOH: The residues free of wax and water soluble succes-
purity of bagasse lignin obtained with this method is 95% related to sively treated with 300 mL of 0.5 M NaOH then filtrated and washed
soluble lignin and the yield of acidolysis lignins isolated from bagasse is with distilled water until the pH of the filtrate was neutral, and then
estimated to be about 8% of biomass treated (Hoareau et al., 2004). dried at 60 °C. The supernatant fluids adjusted to pH 5.5 with 6 M
HCl and then concentrated to about 30 mL under reduced pressure,
3.1.4. Sequential isolation steps by alkaline dioxane and then carried into 120 mL by 95% ethanol to precipitated
Zhang et al. (2013) studied the extraction of lignin fractions derived hemicellulose. The solubilized lignin obtained from the corre-
from ball-milled sugarcane bagasse by alkaline dioxane extraction sponding supernatant by precipitation at pH 1.5–2.0 (lignin fraction
processes. Three steps of extractions, successively, were done using L2).
96% dioxane, 50% dioxane, and 80% dioxane containing 1% NaOH at 5) 0.5% H2O2: The residue from phase 4) treated by 200 mL of 0.5%
boiling temperature. H2O2 at pH 11.5 adjusted with 6 M NaOH then repeated the pro-
cedures in phase 4) to obtain soluble lignin fraction L3.
3.1.4.1. First step extraction with 96% dioxane. Bagasse treated with 6) 1.0, 1.5, 2.0, and 3.0% H2O2: Sequential treatment: same proce-
dioxane solution (96:4, v/v dioxane/water) with ratio 1:20 (g bagasse/ dures in phase 5 repeated with various concentrations of Alkaline
mL solution) for two hours, then filtrated and washed with same Peroxide (1.0, 1.5, 2.0, and 3.0% H2O2) to obtain lignin fraction L4,
solution until the filtrate was clear. The filtrates were concentrated to L5, L6 and L7.
about 50 mL then transferred into 3 vols with 95% ethanol then the 7) 2M NaOH: the last residue is treated by 200 mL of 2 M NaOH at
precipitates of this operation were filtered and washed with 70% 55 °C for 2 h then filtrated and washed with distilled water until the
ethanol and freeze-dried to obtain hemicellulosic fraction (96% pH of the filtrate was neutral, and then dried at 60 °C. The super-
dioxane-soluble); this fraction is called H1. The filtrates were natant fluids adjusted to pH 5.5 with 6 M HCl and then concentrated
concentrated to remove ethanol and resting dioxane then transferred to about 30 mL under reduced pressure, then carried into 120 mL by
into 10 vols of H2O adjusted with 6 M HCl (pH 1.5–2.0). Then, the 95% ethanol to precipitated hemicellulose. The solubilized lignin
precipitates were filtered and washed with acidified water (pH 2.0), obtained from the corresponding supernatant by precipitation at pH
and freeze-dried to obtain the lignin fraction (96% dioxane-soluble), 1.5–2.0 (lignin fraction L8).
this fraction is called L1.
The acid-insoluble lignin fractions obtained from each of the above
3.1.4.2. Second step extraction with 50% dioxane. The solid residues lignin fractions after rinsed by acidified water at pH 2.0 are freeze-
obtained after first treatment (R1) dried for 16 h at 50 °C in a cabinet dried.
oven with air circulation, then, successively, treated with dioxane The total extracted of lignin from the sequential isolation steps was
solution (50:50, v/v dioxane/water) with same ratio and time in the 16.1% on dry based.
first treatment, then filtrated and washed with same solution until the Table 1 shows the percentage of lignin isolated from sugarcane
filtrate was clear. The filtrates were treated using the same method bagasse by different methods. The sequential treatments with various
described above to obtain hemicellulosic fraction (50% dioxane- concentrations of alkaline peroxide and sodium hydroxide released
soluble), which is called H2, and the lignin fraction (50% dioxane- high quantity of lignin. This indicates that these sequential treatments
soluble), which is called L2. of bagasse with alkali and alkaline peroxide are suitable to isolate lignin
from sugarcane bagasse. The method of alkaline pulping with sodium
3.1.4.3. Third step extraction with 80% dioxane. The solid residues hydroxide solution is one of the most suitable methods for isolation of
obtained after second treatment (R2) were refluxed with dioxane lignin from sugarcane bagasse.
solution (80:20, v/v dioxane/water) containing 1% NaOH at boiling
temperature with same ratio and time described above, then filtrated 3.2. Ionic liquid methods
and washed with same solution used in this treatment until the filtrate
was clear. The filtrates were adjusted to pH 5.5–6.0 and treated using Recently, ionic liquids (as: 1-ethyl-3-methylimidazolium acetate
the same methods described above to obtain hemicellulosic fraction ([EMIM]OAc); 1-allylmethylimidazolium chloride ([AMIM]Cl); 1-butyl-
(80% dioxane-soluble), this fraction is called H3, and lignin fraction 3-metylimidazolium chloride ([BMIM]Cl)) used as a solution for pre-
(80% dioxane-soluble), is called L3, (Zhang et al., 2013). treatment, fractionating and removing lignin from lignocellulose bio-
The sequential isolation steps of lignin from sugarcane bagasse with mass (Espinoza-Acosta et al., 2014).
96% dioxane, 50% dioxane, and 80% dioxane containing 1% NaOH at Lan et al. (2011), used the Ionic Liquid (IL) method for fractionation
boiling temperature were extracted 5.10%, 1.35% and 0.75%, respec- of bagasse into cellulose, hemicelluloses, and lignin. This method based
tively. The total yields of lignin were 7.2% based on dried sugarcane on dissolution of bagasse in 1-butyl-3-methylimidazolium chloride
bagasse. In the first step, 70.8% of the total extracted lignin was iso- ([C4mim]Cl) followed by precipitation in acetone/water (9:1, v/v) and
lated. extraction with 3% NaOH solution. This could be briefly described as
following:
3.1.5. Other sequential methods
Sun and his co-workers (Sun et al., 2003) presented eight fractions 3.2.1. Pretreatment
of lignin that have been isolated from sugarcane bagasse as following: Sugarcane bagasse dried, in sunlight, and then cut into small pieces,
ground and screened to pass throw 40–60 mesh and then dried, in a
1) Milling: Sugarcane bagasse first dried in sunlight, milled and cabinet oven with air circulation, for 16 h at 55 °C. This dried extracted
screened to pass through an 0.8 mm sieve. with toluene/ethanol (2:1, v/v) and further pulverized with a vibratory
2) Dewaxed: 10 g of dried powder extracted in a Soxhlet apparatus by ball mill for 72 h.
toluene/ethanol (2:1, v/v) for 6 h, then dried in an oven at 60 °C for
16 h. 3.2.2. Treatment
3) Distilled water: then the obtained powder from phase 2) is im- The ball milled bagasse dissolved in [C4mim][Cl], with ratio 1:50
mersed in 300 mL of distilled water at 55 °C for 2 h under stirring, (w/w), at 110 °C under inert environment with agitation to obtain a
then treated by 3 vols of 95% ethanol to precipitated water extract clear solution, and then add into 200 mL of acetone/water (9:1, v/v)
(water-soluble hemicellulose). The supernatant solution acidified by under strong agitation. The residue 1 (Fig. 3) separated by centrifuga-
6 M HCl to pH 1.5 to obtain soluble lignin fraction L1. tion at 4000 rpm for 15 min, collected and washed by acetone/water

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Table 1
Comparison of various lignin isolation methods from sugarcane bagasse.

Methods Treatment conditions Lignin isolated (% dry References

matter)

Alkaline pulping with sodium hydroxide Hot water pretreatment with ratio 1:10 S/L, at 70–80 °C for 2 h. 13.0 Wahba et al. (2015);
solution Moubarik et al. (2013)
Pulping with 15% NaOH (m/v) and ratio 1:10–1:18 (w/w) at 90–98 °C for 1.5–4 h.
Alkaline pulping with sodium hydroxide Hot water pretreatment at 80 °C. Pulping with NaOH (1:10 m/v) and ratio 1:10 7.2; Costa et al. (2017)
solution (g/mL) at 120 °C for 1 h,
a) Adding three volumes of 95% ethanol (v/v) and acidificated until pH to 1.5 → 5.5;
lignin obtained referred as Lig-Alk
b) oxidation by 14% H2O2 (m/v) at pH 13, for 2 h at 98 °C → lignin obtained referred 6.2
as Lig-Ox
c) acetylation of Lig-Alk under an inert atmosphere and agitating at 28 °C for 2 days
→ lignin obtained referred as Lig-Ac
Extraction by dioxane and hydrochloric Pretreatment by cyclohexane-ethanol (1:1, v:v) for one day and dried at 60 °C, 10.0 Hoareau et al. (2004)
acid and by alkali solution
A) Treatment by dioxane solution and (0.1 N) aqueous hydrochloric acid (8.5:1.5, 8.0
v:v) with ratio (100 g/1L) and heated under nitrogen at 100 °C for 2 h
Treatment by alkali (0.5 M KOH) solution with ratio 50 g/1.5 L under nitrogen at
35 °C for 3.5 h
Alkaline dioxane extraction Sequential steps: 5.1; Zhang et al. (2013)
a) Treatment with dioxane solution (96:4, v/v dioxane/water), ratio 1:20 (g bagasse/ 1.4;
mL solution) for 2 h.
b) Treatment with 50% dioxane (50:50, v/v dioxane/water), ratio 1:20 (g bagasse/ 0.8
mL solution) for 2 h.
c) Treatment with 80% dioxane (80:20, v/v dioxane/water) containing 1% NaOH at
boiling temperature, ratio 1:20 (g bagasse/mL solution) for 2 h.
Sequential treatments with various Sequential treatments steps with distilled water, 0.5 M NaOH, 0.5, 1.0, 1.5, 2.0, and 0.5, 9.5, 2.7, 0.6, 1.0, Sun et al. (2003)
concentrations of alkaline peroxide 3.0% H2O2 at pH 11.5, and 2 M NaOH at 55 °C for 2 h 0.9, 0.5, and 0.4
and sodium hydroxide

(9:1, v/v) to eliminate [C4mim]Cl, and then dried and extracted with aromatic ring). Functional groups related to lignin in components of
3% NaOH solution at 50 °C with ratio 1:25 (g/mL) for 45 min. lignocellulose are aromatic ring, hydroxyl group; carbon to carbon
The filtrate 1 collected and concentrated by evaporation to remove linkage and ether (glucosidic) linkage.
acetone and then added into 250 mL of acidified water (pH 2.0) under Cellulose fraction, (C6H10O5)n, is a long-chain polymer poly-
stirring. The residue 2 centrifuged and washed with acidified water (pH saccharide, sometimes so-called “glycans” carbohydrate of beta-glu-
2.0) to obtain acetone soluble lignin. Filtrate 2 reused after treated as cose, which forms the primary structural component of plants.
recycled IL (Fig. 3). Hemicellulose fraction, (C5H8O4)n, is similar to cellulose but is less
The cellulose obtained (residue 3) from residue 1 after treatment by complex; it consists mainly of pentosic sugars and sugar acids.
3% sodium hydroxide solution was washed three times with distilled Lignin (lignum) is a complex polymer, [(C9H10O3(OCH3)0.9–1.7]n,
water. The filtrate 3 was treated with 4 M hydrochloric acid (HCl) and combines cellulose and hemicellulose (Akhtar et al., 2015).
precipitated in 3 vols using 95% ethanol to obtain hemicellulose (re- Many researchers have established that the lignin derivative from
sidue 4). The filtrate 4 was concentrated under reduced pressure to non-wood biomass is made up of three principal monolignols units,
remove ethanol and precipitated in acidified water (pH 2.0) to obtain these polymers are derived from the p-hydroxycinnamyl alcoholmo-
alkaline lignin (residue 5). nomers. Three principal monolignols subunits are p-Hydroxyphenyl
The fractionations of bagasse obtained from this method are 36.78% subunit (H), Guaiacyl subunit (G), and Syringyl subunit (S). They are
cellulose, 26.04% hemicelluloses, 10.51% lignin and 26.67% of bio- linked between them through different types of linkages. They are p-
mass lost. coumaryl alcohol (C9H10O2), coniferyl alcohol (C10H12O3), and sinapyl
The following Table (Table 2) shows the percentage of lignin re- alcohol (C11H14O4), or trans-p-coumaryl, trans-coniferyl, and trans-si-
moved from sugarcane bagasse by different ionic liquid and treatment napyl alcohols (Sun et al., 2003; Arni et al., 2007; Arni et al. 2010a,b;
conditions. The 1-(4-sulfobutyl)-3-methylimidazolium hydrosulfate is Lino et al., 2015). Due to the presence of H lignin in addition to G and S,
the best method that could be used to remove all lignin. The 1-Ethyl-3- lignin in bagasse differs from those in hardwood (Brandt et al., 2013).
methylimidazolium sodium alkylbenzenesulfonate ([EMIM][Na] Bagasse is an excellent resource material for production of chemical
[ABS]) is the second best method that removed 93%. compounds (Fig. 4), such as arabinose, glucose, furfural (Lavarack
et al., 2002), lactic acid (Laopaiboon et al., 2010), xylose (Boussarsar
4. Composition and structure of sugarcane bagasse et al., 2009), and polymetric materials such as plastics (Doherty et al.,
2007).
The chart in Fig. 4 shows the chemical compositions of sugarcane The lignin fraction contains phenolic acids and aldehydes which
bagasse that can be separated from one or more of its major compo- have chemical compounds such as p-hydroxybenzoic acid, p-hydro-
nents, such as cellulose, hemicellulose, and lignin. This biomass mate- xybenzaldehyde, vanillic acid, vanillin, syringic acid, syringaldehyde,
rial is a natural complex biopolymer structure of carbohydrates, che- acetovanillone, acetosyringone, p-coumaric acid, and ferulic acid (Sun
mically has four important types of bonds between the monomer units: et al., 2003; Arni et al., 2007; Arni et al., 2010a,b). In addition, the
ester bonds, ether bonds, hydrogen bonds and carbon-to-carbon bonds sugar of lignin fraction has rhamnose, arabinose, xylose, mannose,
(Harmsen et al., 2010). Ester bonds are between lignin and poly- galactose and glucose (Sun et al., 2003; Arni et al., 2007).
saccharides (cellulose and hemicellulose), ether bond are among the Lignin is rich with natural aromatic organic compounds such as p-
functional groups (as hydroxyl group), hydrogen bonds that is between comaric acid (p-CA), ferulic acid (FA), syringic acid (SA), vanillin (V)
the cellulose polymer chains, and carbon-to-carbon bonds (as in (Arni et al., 2007; Arni et al., 2010a,b).

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S.A. Arni Industrial Crops & Products 115 (2018) 330–339

Bagasse
Extracted with toluene-
ethanol (2/1, v/v) for 6 h
Dewaxed
Bagasse

Ball milled for 72 h

Ball milled bagasse

Dissolved in IL

Bagasse/IL soluƟon
Regenerated with
acetone/water(9/1, v/v)

Filtrate 1 Residue 1
(Carbohydrate-rich material)
Evaporated to remove acetone Extracted with 3%
Acetone recycle
Precipitated in acidiĮed water NaOH for 45 min
(pH 2.0)

Filtrate 3 Residue 3
Filtrate 2 Residue 2 Adjusted to pH 6.8 (Cellulose)
(Acetone soluble lignin) Precipitated with 3
volumes of ethanol

Filtrate 4 Residue 4
(Hemicellulose)
Evaporated to remove ethanol
Precipitated in acidiĮed water
(pH 2.0)

Filtrate 5 Residue 5
(Alkaline lignin)

Fig. 3. Schematic illustration of Ionic Liquid method (adapted from Lan et al., 2011).

5. Quantity of sugarcane lignin fraction between sugar can bagasse wood and non-wood materials.
Table 4 shows the fractions of sugarcane bagasse collected from
The quantity of sugarcane lignin fraction depends on the method of literature and the chart (Fig. 4) shows its chemical composition based
extraction. The determination of lignin content in biomass is usually on the mass balance.
determined by the Klason method. The Klason method or treatment by On the other hand, the percentage of lignin fraction does not highly
concentrated sulphuric acid, usually 72%, is used to separate the in- depend on the cultivation places. The range that above mentioned
soluble lignin from lignocellulosic materials. The fraction of lignin se- which treated by H2SO4 72%, it has 22% as an average over 60 samples
parated by this method is called “Klason lignin”. The quantity of su- collected from different places (Rocha et al., 2015a).
garcane lignin fraction (Klason lignin) is in the range of 17–32% of Other methods are based on the soluble lignin, which could be ex-
lignocellulosic bagasse on dry weight of biomass (Table 3). Table 3 tracted and isolated using organic solvents (such as acetic acid, ethanol,
shows the range of lignocellulosic materials. It provides a comparison dioxane, methanol, etc.), ionic liquids (IL) and alkaline solutions. The

Table 2
Comparison of ionic liquid methods used to remove lignin from sugarcane bagasse.

Ionic liquid Treatment conditions Lignin removed (%) References

1-Ethyl-3-methylimidazolium sodium alkylbenzenesulfonate ([EMIM][Na] 170–190 °C, 30–120 min 93.00 Tan et al. (2009)
[ABS])
1-butyl-3-methylimidazolium chloride ([C4mim]Cl) 110 °C, 15 min under a nitrogen atmosphere 54.62 Lan et al. (2011)
with agitation
1,3-dimethylimadazolium dimethyl phosphate ([Mmim][DMP]) 120 °C, 120 min n.d. Bahrani et al. (2015)
1-Ethyl-3-methyl imidazolium acetate ([EMIM][OAc]) 165 °C, 10 min 34.00 Li et al. (2011)
([EMIM][OAc]) 120 °C, 30 min 32.00 Qiu et al. (2012)
1-butyl-3-methylimidazolium methyl sulfate ([BMIM][MeSO4]) (7% H2SO4) 125 °C, 2 h 26.00 Diedericks et al. (2012)
1-(4-sulfobutyl)-3-methylimidazolium hydrosulfate ([BMIM][SO3] [HSO4]) 200 °C, 30 min 100.00 Long et al. (2013)
(ethanol/water)

n.d. = not determined.

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S.A. Arni Industrial Crops & Products 115 (2018) 330–339

Fig. 4. Chemical composition of bagasse based on the mass balance (adapted from Carvalho, 2015).

solubilized lignin is then recovered from solution by precipitation with Table 4

acids (Mancera et al., 2010). The solvents that solubilizes the lignin Fractions of sugarcane bagasse collected from literature.
from biomass, in different quantities, depend on the applied techniques
Values are in percentage, w/w, on dry weight
and the aim of study. The following are some examples of the quantities
extracted and isolated by these procedures: References Cellulose Hemicellulose Lignin Extractive1 Ash

a a a a
Rocha et al. (2015a) 42.19 27.60 21.56 5.63 2.84a
a) The range of percentage of lignin fraction on dry weight is between
Canilha et al. (2011) 45.00 25.80 19.10 9.10 1.00
9%, for that treated by NaOH 4%, and 30% for those treated by Sun et al. (2003) 43.60 33.50 18.10 0.80 2.30
H2SO4 1% (Rezende et al., 2011). Hoareau et al. (2004) 55.20 16.80 25.30 n.d. 1.10
b) On the other hand, the total yield of lignin is 7.2% based on dried Ezhumalai and 50.00 25.00 25.00 n.d. n.d.
biomass treated by alkaline dioxane extraction processes. The 96% Thangavelu (2010)
Yao et al. (2015) 45.28 22.13 22.39 7.11b 1.01
dioxane process gives a 70.8% of the total extracted lignin that it
Pereira et al. (2011) 45.40 28.70 23.40 n.d. 2.70
was isolated (Zhang et al., 2013). Rabelo et al. (2011) 40.50 24.50 26.40 7.00c 1.60
c) The yields of lignin that be treated by dioxane and hydrochloric acid Ayeni et al. (2015) 35.28 33.28 25.20 2.14 4.10
and by alkali (KOH) solution are 10% and 8%, respectively, re- Average value 44.72 26.37 22.94 3.53 1.85
ference to Klason lignin (Hoareau et al., 2004). 1
Mainly of the extractive is wax.
d) The total yield solubilized lignin that has been isolated from the a
Average of 60 samples.
sugarcane by sequentially sodium hydroxide and alkaline peroxide b
Benzene–alcohol extract (%) [the 1% Sodium hydroxide extract (%) is 24.97].
is 89.0% of the original lignin bagasse (Sun et al., 2003). n.d. = not determined.

The average value of lignin fraction is about 23% of biomass

(Table 4), this value is similar to that found by Rocha et al. (2015a) and (Kirk-Othmer, 2005); it has an average of 23% of biomass compared to
it is independent of the cultivation zones. 16.2% of non-wood (Table 5). This comparison of sugarcane bagasse
with various non-wood plants reveals that this material has the highest
content of lignin and a lowest content of ash than all non-wood biomass
6. Comparison between lignin fractions in sugarcane bagasse and (Table 5).
in non-wood biomass The highest amount of lignin in bagasse could be considered as an
economic advantage towards deriving chemical resources from agro-
Generally, non-woods contain less lignin, but the percentage of industrial waste residues.
Klason Lignin of bagasse has a major content among non-wood biomass

Table 3
Composition range of lignocellulosic materials.

Values are in percentage

Biomass species Cellulose Hemicellulose Lignin Extractive Ash References

Hardwood 40.0–55.0 24.0–40.0 16.0–25.0 2.0–8.0 0.2−0.6 Kumar et al. (2009); Demirbas et al. (2009); Carbolea (2017)
Softwood 40.0–50.0 24.0–35.0 25.0–35.0 1.0–5.0 0.2−0.6 Kumar et al. (2009); Demirbas et al. (2009); Carbolea (2017)
Sugarcane 32.0–45.0 20.0–32.0 17.0–32.0 1.0−9.0 1.0−3.0 Kurakake et al. (2001); Neureiter et al. (2002); Sun et al. 2003; Hoareau et al. (2004); Martín
bagasse et al. (2007); Area et al. (2009); Ezhumalai and Thangavelu (2010); Da Silva et al. (2010);
Canilha et al. (2011); Pereira et al. (2011); Rabelo et al. (2011); Rocha et al. (2011); Novo
et al. (2011); Vallejos et al. (2012); Rocha et al. (2015b); Yao et al. (2015)
Non-wood 29.2–73.8 9.9–38.8 7.5–26.1 0.8−8.3 0.9–14.0 Shatalov et al. (2001); Cordeiro et al. (2004); Hoareau et al. (2004); Fiserova et al. (2006);
biomass Abdul Khalil et al. (2012); Aysu and Küçük (2014); Ferrer et al. (2015)

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S.A. Arni Industrial Crops & Products 115 (2018) 330–339

Table 5
The composition of some non-wood biomass collected from literature.

Biomass Cellulose Hemicellulose Lignin Extractive Ash References

Values are in percentage

Arundo donax (Giant reed: Arundo donax L.) 29.20 32.10 20.90 n.d. 4.80 Shatalov et al. (2001)
Banana (Musa paradisiaca) pseudo-stems 40.00 25.20 12.70 n.d. 14.00 Cordeiro et al. (2004)
Amaranth (Amaranthus) 32.00 26.10 13.20 n.d. 12.00 Fiserova et al. (2006)
Orache (Atriplex) 36.00 38.80 19.50 n.d. 2.00 Fiserova et al. (2006)
Curauá (Ananas lucidus) 73.60 9.90 7.50 n.d. 0.90 Hoareau et al. (2004)
Ferula orientalis L. 45.60 22.57 26.11 0.87 4.85 Aysu and Küçük (2014)
Wheat (Triticum aestivum) straw 30.60 32.30 16.80 9.80 5.00 Silva-Fernandes et al. (2015)
Bamboo (Bambusa vulgaris) fiber 73.83 12.49 10.15 3.16 n.d. Abdul Khalil et al. (2012)
Oil palm (Elaeis guineensis) empty-fruit-bunch (OPEFB) 62.90 28.00 18.80 3.70 1.30 Law et al. (2007)
Barley (Hordeum vulgare) straw 36.20 28.30 16.10 8.30 9.32 Ferrer et al. (2015)
Average value 46.00 25.60 16.20 2.60 5.40

n.d. = not determined.

7. Conclusion Brandt, A., Gräsvik, J., Hallett, J.P., Welton, T., 2013. Deconstruction of lignocellulosic
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