Renewable Energy 146 (2020) 56e65

Contents lists available at ScienceDirect

Renewable Energy
journal homepage: www.elsevier.com/locate/renene

Efficient hydrolysis of Babool wood (Acacia nilotica) to total reducing

sugars using acid/ionic liquid combination catalyzed by modified
activated carbon
Uplabdhi Tyagi, Neeru Anand*, Dinesh Kumar
University School of Chemical Technology, Guru Gobind Singh Indraprastha University, India

a r t i c l e i n f o a b s t r a c t

Article history: This study aims to examine the potential of Babool wood (Acacia nilotica) as an alternative and sus-
Received 28 October 2018 tainable resource to produce value added chemicals and/or useful intermediates like sugars. The per-
Received in revised form formance of Babool wood digestability and hydrolysis to sugars was compared using three acids: H2SO4/
23 June 2019
H3PO4/HCl and ionic liquid [Bmim] Cl catalyzed by modified activated carbon. Hydrolysis using sulphuric
Accepted 25 June 2019
acid treated Babool wood leads to the formation of total reducing sugar (TRS) ranging from 53.34% to
Available online 26 June 2019
83.67% yield under different conditions. Babool wood treated with acid was characterized using Fourier
Transformation Infrared Spectroscopy, X- Ray Diffraction and Lignocellulosic compositional analysis.
Keywords:
Acacia Nilotica
Further, the effect of process variables such as acid strength, acid concentration, acid to Babool wood
Hydrolysis ratio, Babool wood particle size, hydrolysis time, and temperature on the TRS yield was explored.
Particle size Maximum TRS yield was observed to be 83.67% in a reaction time of 60 min using
80 þ 100 mesh of
Activated carbon Babool wood at 393 K. Kinetic results were successfully simulated with literature model (R2 > 0.9) for
Acid/ [Bmim] Cl ionic liquid treatment rate of formation of sugar. This study provides a single step approach for Babool wood hydrolysis to
sugars.
© 2019 Elsevier Ltd. All rights reserved.

1. Introduction expansion and microbial pretreatment but due to challenges and

The use of petrochemicals has increased exponentially in last
few decades but depletion of conventional resources has forced
researchers to look for alternative sustainable sources. Lignocellu-
losic materials are the most efficient renewable clean resource due
to its potential stability and carbon neutrality [1,2]. Significant ef-
forts are being made globally for the conversion of lignocellulosic
components to hydrocarbons such as total reducing sugar, 2, 5-
Dimethyl furan, Levulinic acid, 2, 5 Furan dicarboxylic acid [3e5].
Complex structure of hemicellulose-lignin along with highly or-
dered inter and intra hydrogen network of cellulose is a hindrance
for the hydrolysis of lignocellulosic biomass [6e10]. To overcome
the recalcitrant nature of lignocellulosic material, pretreatment and
hydrolysis is important for production of value added products
[6,11e13]. Literature reports various pretreatment techniques such
as steam explosion, liquid hot water pretreatment, ammonia fibre
* Corresponding author.
E-mail addresses: uplabdhityagi200@gmail.com (U. Tyagi), neeruanand@ipu.ac.
in (N. Anand), dinesh.usctfac@ipu.ac.in (D. Kumar).
disadvantages associated with these processes such as excessive
degradation of physiochemical properties of cellulose and hemi-
cellulose, high energy input and slow reaction time required
appropriate and potential candidate for disintegrating biomass
matrix [14e16]. Utilization of ionic liquids and/or mineral acids
pretreatment (dilute or concentrated) has gained attention and are
commonly used methods to reduce the crystallinity of biomass
matrix [17e19].
The hydrolysis of bamboo biomass in ionic liquid media cata-
lyzed with chitosan based solid acid catalyst has been reported and
maximum TRS yield was found to be 73.42% in 24 h at 120  C [3].
Also, the pretreatment of softwood using [Bmim] Cl has been
studied and 78% of glucose yield was reported at 130  C in 15 h [20].
These studies conclude that ionic liquid helps in breaking the
recalcitrance nature of biomass but requires long reaction time.
Some studies have been reported using only mineral acids. Sul-
phuric acid hydrolysis on olive biomass has been studied and 17.2%
of TRS yield was observed in a reaction time of 4 h at 90  C [21].
Also, the pretreatment effect on wheat straw using 5 wt% of H2SO4
at 50  C was reported and maximum glucose yield of 96% was

https://doi.org/10.1016/j.renene.2019.06.150
0960-1481/© 2019 Elsevier Ltd. All rights reserved.
 U. Tyagi et al. / Renewable Energy 146 (2020) 56e65
observed in a reaction time of 72 h [22]. These studies also indicate
that long reaction time is a major drawback for biomass hydrolysis.
Literature reports that combination of ionic liquid and mineral
acid has a synergistic effect on the hydrolysis process [2,23e25].
The combined effect of [C4mim] Cl and dilute hydrolchloric acid
was studied and maximum TRS yield of 4% in 0.5 h was observed
using cornstalk and 85% TRS yield in 1 h using pinewood at 100  C
[26]. Hydrolysis of Bamboo biomass was also studied using dilute
hydrochloric acid in [Bmim] Cl media and maximum TRS yield of
67.1% was obtained in a reaction time of 4 h at 100  C [1].
Some studies reported utilization of heterogeneous catalyst and
ionic liquid for the hydrolysis of lignocellulosic biomass. Literature
reports that chemical treatment of activated carbon using mineral
acids provide appropriate amount of brØnsted acid and hence leads
to fast hydrolysis [27,28]. Switchgrass hydrolysis catalyzed by
activated carbon modified with sulphonic acid was reported and
maximum glucose yield of 16.91% was observed in a reaction of
15 min at 90  C [29]. Also, hydrolysis of microcrystalline cellulose
catalyzed by sulphuric acid treated activated carbon in [Bmim] Cl
medium was also studied and maximum yield of TRS (44.57%) and
5-Hydroxymethyl Furfural (36.33%) was observed in a reaction time
of 1 h at 120  C [28].
In the present work, combination of acid/IL catalyzed by
modified activated carbon was studied on hydrolysis of Babool
(Acacia Nilotica) wood for the production of sugars. Also, a
comparative study was conducted to examine the effect of acid
strength using different acids namely; H2SO4, H3PO4 and HCl on
hydrolysis in [Bmim] Cl ionic liquid and modified activated carbon.
Lastly, kinetic study was conducted to determine rate of formation
of TRS.
2. Materials and methods
2.1. Materials
Babool wood was acquired from GGSIP University, New Delhi,
Glucose standard solutions (1%), 3, 5 Dinitro Salicylic Acid, 1-Butyl-
3-Methylimidazolium chloride, Sulfuric acid, Phosphoric acid and
Hydrochloric acid were purchased from Central Drug House Pvt.
Ltd. (CDH) Vadodara, Gujarat. Activated carbon (AC) was purchased
from Merck Life Sciences Pvt. Ltd, Darmstadt, Germany.
2.2. Methodology
2.2.1. Screening of Babool wood
The Babool wood (Acacia nilotica) was thoroughly washed with
distilled water for the removal of impurities followed by drying in
hot air oven at 100  C for 12 h. Dried Babool wood was crushed in
ball mill and sieved to fractions with particle size ranging from
(i)
20 mesh (ii)
20 to þ40 mesh (iii)
40 to þ60 mesh (iv)
60
to þ80 mesh (v)
80 to þ100 mesh (vi)
100 to þ120 mesh and
used as feed.
2.2.2. Preparation of catalyst
Modified activated carbon was prepared and characterized as
reported in our previous work [28] and denoted as ACS. The pro-
cedure is as follows: 20 g of activated carbon was mixed thoroughly
using 18 M of sulfuric acid in 100 ml of deionised water and
refluxed for 4 h at 75e80  C. The resultant solution was washed
thoroughly using deionised water to prevent ions elution in reac-
tion system. Finally, resultant modified activated carbon (ACS) was
filtered through vaccum filter and dried for 12 h at 120  C.
2.2.3. Characterization of Babool wood
Untreated and acid treated Babool wood using three different
57
acids namely; H2SO4, H3PO4 and HCl were characterized using
Fourier Transformation Infrared Spectroscopy (FT-IR) and X- Ray
Diffraction (XRD). FT-IR analysis was conducted to determine
change in functional groups before and after acid treatment. A
reflectance spectrum was performed for wavenumber ranging
from 400 to 4000 cm
1 with resolution of 4 cm
1 using Ther-
moscientific Nicolet IS50 Fourier transform spectroscopy,
Thermo Fisher Scientific, Massachusetts, United States. The
crystallinity of untreated and acid pretreated biomass was
measured using X- Ray Diffraction (Xpert pro PAN Analytical
model), Malvern Panalytical Ltd. United Kingdom. The diffracted
intensity of Cu Ka radiation generated at 40 kV and 15 mA was
recorded with diffracted angle ranging from 10 to 90 with
scanning speed of 2 /minute. Lignocellulosic composition was
determined using TAPPI (Technical Association of the Pulp and
Paper Industry) standards.
2.2.3.1. Compositional analysis. Extractives present in Babool wood
were determined using solvent extraction method according to
TAPPI 204 cm-97 [30]. Samples were thoroughly washed with
distilled water for removing impurities and dried at 100  C for 12 h
in hot air oven. Water soluble compounds such as nitrogeneous
materials, inorganic and non-structural compounds were deter-
mined using 100 ml of distilled water for 6 h in a soxhlet apparatus.
The sample was then dried again at 105  C for 2 h and was referred
as water soluble compounds. Ethanol extractives were determined
using another set of soxhlet extraction for the removal of waxes and
chlorophyll using 100 ml of ethanol (95%) for 6 h and the final
extractive content was measured as total mass loss during the
procedure [31]. The sample was then removed from soxhlet
apparatus and dried again at 105  C for 2 h and referred to as
ethanol extractives.
For determination of total solids, Babool wood sample was dried
at 100  C for 12 h in hot air oven according to the National
Renewable Energy Laboratory procedure (ASTM E1756-01 and T412
om-02) [32]. As per the procedure, the sample was heated at 105  C
in hot air oven for 4 h and then allowed to cool at room temperature
to determine total solid percentage in the Babool wood.
The total content of cellulose present in Babool wood, based on
TAPPI standard, was determined as the amount of a-cellulose
which is soluble in 17.5% NaOH solution. Analysis of a-cellulose was
conducted by stirring 1 gm of biomass in beaker with 20 ml of 17.5%
NaOH solution at 30  C for 45 min in water bath. Then, 10 ml of
distilled water was added in to the solution and shaken again for
another 15 min. Finally, the solution was washed with 10 ml of 10%
acetic acid and filtered using whatman filter paper. The obtained
sample (a-cellulose) was dried in hot air oven for 12 h at 80  C and
weighed. Similarly, total content of holocellulose in Babool wood
was determined as the sum of hemicellulose and cellulose. In this
analysis, initially 1 gm of Babool wood was treated with 30 ml of
distilled water that contains 0.04 ml of acetic acid and 0.4 g of so-
dium chlorite for 60 min at 75  C. Further, same proportion of acetic
acid and sodium chlorite (0.04 ml; 0.4g) was added in the mixture
successively in every 60 min for 3 h. Finally, the obtained sample
(holocellulose) was filtered and dried in hot air oven for 12 h at
80  C and weighed [24].
Total content of lignin in Babool wood was determined as klason
lignin in the form of acid insoluble residue according to TAPPI
method; T 222 om-02 [32]. Initially, 1 g of Babool wood was dis-
solved in 15 ml of 72% H2SO4 and the mixture was stirred at 20  C
for 4 h. Then, sample was diluted with water up to 3% H2SO4 and
subsequently 575 ml of water was added in to the mixture and
refluxed for 4 h. Finally, samples were dried in hot air oven at 105  C
for 5 h and weighed [31].
58 U. Tyagi et al. / Renewable Energy 146 (2020) 56e65
2.2.3.2. Proximate analysis. The percentage of moisture content in
the Babool wood was determined according to National Renewable
Energy Laboratory procedure ASTM E1756-01 and T412 om-02 by
placing the sample in hot air oven at 105  C for 4 h [32]. To deter-
mine the percentage of ash content in the biomass, sample was
placed in muffle furnace at 575  C for 24 h (ASTM Standard Method
Number E1755-01). The percentage of volatile matter in biomass
sample was determined according to ASTM D 3175-07 method [32].
1 g of Babool wood was placed in muffle furnace at 950  C for
10 min. Finally, the sample was removed from the furnace and loss
of weight accounts the amount of volatile matter present in sample.
Finally, total carbon was determined by subtracting the percentage
sum of moisture content, ash content and volatile matter from 100
[24].
2.2.4. Experimental procedure for Babool wood hydrolysis
Experimental procedure includes pretreatment of Babool wood
using either H2SO4 or H3PO4 or HCl for delignification followed by
hydrolysis using [Bmim] Cl catalyzed by modified activated carbon
(ACS) in a single step. In a typical run, sieved Babool wood (0.05 g)
was presoaked in a glass vial using dilute acid (H2SO4 or H3PO4 or
HCl) of concentrations ranging from (0.25e1.25 M) for 30 min with
a constant stirring at 500 rpm at room temperature. The pretreated
biomass was hydrolyzed using 2 g of ionic liquid [Bmim] Cl in the
reaction system. To this mixture, 0.05 g of modified activated car-
bon (ACS) was added and refluxed at temperatures ranging from
100 to 200  C in oil bath and for reaction time ranging from 30 to
150 min. Finally, quantitative analysis of TRS content was per-
formed by collecting hydrolyzate at regular intervals of time. The
hydrolyzate was quenched in cold water for 15 min to stop further
reaction and centrifuged at 4000 rpm for 5 min [28]. All the ex-
periments were conducted in triplicate and the experimental data
with error bars are shown in graphs with maximum standard
deviation ± 2%.
2.2.5. Recyclability study
Recovery and reusability studies of ionic liquid was also con-
ducted to make the process economically viable. Experiments were
conducted using 0.05 g of Babool wood catalyzed by 0.05 g of
modified activated carbon in 2 g [Bmim] Cl medium at a reaction
temperature of 120  C in 60 min. After the completion of reaction
ionic liquid was recovered by adding 10 ml of 50% (w/w) NaOH
solution as reported in our previous work [28]. The obtained so-
lution was stirred for 20 min at 500 rpm and then centrifuged at
4000 rpm for phase separation containing upper layer as [Bmim] Cl
rich and bottom layer as NaOH rich. Finally the recovered ionic
liquid was used with fresh biomass loading and catalyst under
same reaction conditions.
2.3. Product analysis
2.3.1. Total reducing sugar analysis
Analysis of total reducing sugar was performed by UVeVis
Spectrophotometer using Dinitrosalicylic acid (DNS) method [33].
In a standard procedure, supernatant (1 ml) and DNS reagent (3 ml)
were mixed and heated for 5 min in boiling water. The resultant
solution was quenched to ambient temperature and finally 6 ml of
water was added to the solution [28]. The color intensities were
measured at 540 nm using UVeVis Spectrophotometer (UV-2900
model), Hitachi, Ltd. Japan. The unknown TRS concentration in the
hydrolyzate was calculated based on calibration curve drawn by
known concentrations of standard glucose. Total reducing sugar
mass and yield were calculated as follows [3]:
 
M0
MT ¼ M1  (1)
Ms
M1 ¼ TRS concentrationðmg=LÞ  V1 ðLÞ (2)
MT
TRS Yield ¼  100% (3)
MBW  A  1:1
where MT is the total mass of TRS, M1 is the TRS mass in the reaction
sample, Mo is the total resultant solution, MS is the total sample
mass, MBW is the mass of Babool wood i.e 50 mg and A is the total
weight percentage of polysaccharides in lignocellulosic materials.
For Babool wood (mass%) A ¼ 48.5% (cellulose) þ 18.3%
(hemicellulose) ¼ 66.8%
3. Results and discussion
3.1. Characterization of Babool wood
3.1.1. FTIR analysis
The IR analysis of untreated and acid treated Babool wood
shown in Fig. S1 was performed to determine the conformational
and physico-chemical changes. In general, the overall spectra of
untreated Babool wood do not exhibit major shift in peaks but acid
treated Babool wood especially H2SO4 treated wood exhibit major
derivatization of functional groups. Broad and wider peaks around
3325-3401 cm
1 attributes to O-H stretching vibration in case of
untreated wood, H3PO4 and HCl treated wood whereas H2SO4
treated Babool wood possess sharp peaks in the range of
3746e3854 cm
1. This is due to stronger vibration of O-H stretching
and hence better disruption of cellulose hydrogen bonding
network. Also, sharp and wide peaks near 2803-2926 cm
1 con-
firms medium symmetric CH stretching of CH3 and CH2 group in
case of untreated, H3PO4 and HCl treated wood whereas strong
symmetric stretching attributes dominance of amorphous region in
case of H2SO4 treated wood [34]. Bands near 1620-1520 cm
1
observed for H2SO4 treated wood, represents the presence of amide
I and II group and strong stretching of C¼O group whereas disap-
pearance of these peaks were observed in other cases [35]. Sharp
peaks near 1454-1449 cm
1 and 1182-1173 cm
1 in case of H2SO4
and H3PO4 treated wood represents strong CH2 bending that occurs
due to disruption of cellulose matrix, resulting in high TRS content
as compared to HCl treated wood. Also, band near 1098-1011 cm
1
in case of H2SO4 and H3PO4 acid treated wood represents C-O and
C-C group stretching at b- 1, 4 glycosidic bonds that show reduction
of crystallinity in biomass [36]. Appearance of peak around 710-
518 cm
1 only in case of H2SO4 and H3PO4 treated wood attributes
to glucan equatorial b-anomer C-H bending and presence of
mannan band represents disruption of anomeric unit of b- 1, 4
glycosidic bonds for TRS production [35]. FT-IR analysis suggests
that disruption of lignin occurs fastly in case of acid treated wood
especially in case of H2SO4 that improves TRS production as
compared to untreated Babool wood.
3.1.2. X-Ray Diffraction (XRD) analysis
X-Ray Diffraction (XRD) was performed to investigate the
structural changes in untreated and acid treated Babool wood. The
signal smoothening of all the integrated peak areas were processed
in Origin Pro 8.5.1 software using SavitzkyeGolay method. It can be
observed from Fig. S2 that untreated Babool wood has broad and
weak peak at 2q near 22.02 with high intensity representing
highly crystalline structure [37]. However, a significant change was
observed in case of H2SO4 treated Babool wood representing sharp
 U. Tyagi et al. / Renewable Energy 146 (2020) 56e65
and low intensity peak at 2q near 26.45 . The sharp peak attributes
the transformation of highly crystalline region to more amorphous
region that occurred due to disruption of lignin [37]. In comparison
to H2SO4 treated Babool wood, H3PO4 and HCl treated Babool wood
with broader and high intensity peak at 2q near 24.91 and 21.99
shows less reduction in transformation of crystalline region to
amorphous region.
3.1.3. Compositional analysis
The sieved Babool wood was characterized for compositional
fractions and proximate analysis using TAPPI standards and results
are shown in Table 1. It is observed from Table 1 that Babool wood
contains 48.5% cellulose and 18.3% hemicellulose, which makes it a
potential candidate for producing value added chemicals.
3.2. Effect of acid strength and acid concentration on Babool wood
hydrolysis
Experiments were conducted to examine the effect of acid
strength using: H2SO4, H3PO4 or HCl on pretreatment and subse-
quent hydrolysis of Babool wood with varying particle sizes using
ionic liquid [Bmim] Cl catalyzed by modified activated carbon. It
was observed from Fig. 1 that H2SO4 treated Babool wood gave
maximum TRS yield of 73.67% for up to
20 mesh and 82.34%
for
100 þ 120 mesh in comparison to H3PO4 or HCl treated Babool
wood. In addition, effect of acid concentration in the range of from
0.25 M to 1.25 M was also investigated. It was noticed from Fig. 1
that on increasing molar concentration of each acid from 0.25 M
to 1.25 M, TRS yield increased. This can be due to the fact that on
increasing acid concentration from 0.25 M to 1.25 M crystallinity of
biomass decreases rapidly due to the disruption of lignin structure
that results in high TRS yield. In dilute acid treatment of Babool
wood protonation of polysaccharides releases cyclic carbonium ion
due to which free sugars get liberated and hence high TRS yield
[24]. Literature reports that sulphuric acid pretreatment enhances
digestability of cellulose and increase in sugar content [38e40]. The
order of acids for pretreatment of Babool wood on the basis of
decreasing TRS yield is H2SO4 > H3PO4> HCl. These results are also
in agreement with XRD data that reveals fast disruption of lignin
structure in case of H2SO4 pretreatment. Literature reports that
additions of dilute acid helps in breaking inter and intra molecular
hydrogen bonding that increases surface area [6]. This provides
sufficient contact of biomass with acid that reduces crystallinity of
cellulose and produces high yield of TRS. In addition, pka (acid
dissociation constant) value for H2SO4 is (1.92); for H3PO4 is (2.12)
whereas for HCl value of pka is (
7). This indicates that higher the
strength of acid, more is the accessibility towards biomass for
producing high yield of TRS.
In the present study, combination of dilute acid/ionic liquid
[Bmim] Cl catalyzed by modified activated carbon was used for
hydrolysis of TRS. Dilute acid and ionic liquid [Bmim] Cl promotes
the disintegration of cellulose and hemicellulose molecules of
biomass matrix. It may be due to the exposure of Babool wood to
Hþ ions of acid and dissociated Cl
ions including the electron rich
Table 1
Compositional and proximate analysis of Babool wood.
Compositional analysis
Characterstics Composition (%)
Water soluble extractives 6.10
Ethanol extractives 6.20
Lignin 20.9
Cellulose 48.5
Hemi-cellulose 18.3
59
Fig. 1. Effect of acid strength over different particle size of Babool wood on TRS yield.
(a) H2SO4 (b) H3PO4 (c) HCl. (Reaction Time ¼ 60 min, IL ¼ 2g, Babool wood
Loading ¼ 0.05g, Catalyst Loading ¼ 0.05g, Temp. ¼ 393 K, RPM ¼ 500, Acid
quantity ¼ 500 ml).
aromatic p system of [Bmim]þ in [Bmim] Cl that weakens b-1, 4
glycosidic linkage and releases more sugar molecules. In addition,
these results reveal that particle size of biomass also plays a role on
Babool wood hydrolysis. It was found that on decreasing particle
size from coarse size to fine particles, mass transfer enhances and
lowers diffusion resistance coefficient resulting in fast hydrolysis
[41]. It was observed that TRS yield was found to be unaffected
using particle size of
100 to þ120 mesh. Hence, further experi-
ments were conducted in the range of
80 to þ100 mesh using
H2SO4 treated Babool wood.
3.2.1. Effect of acid/Babool wood ratio
Experiments were conducted to optimize amount of H2SO4 acid
for 0.75 M and 1 M acid concentration using appropriate liquid
(acid) to solid (Babool wood) ratio. Fig. 2 summarizes the effect of
increasing acid (liquid) to Babool wood (solid) ratio ranging from 10
to 40 on TRS yield catalyzed by modified activated carbon (ACS) at
393 K. Fig. 2 revealed that for 0.75 M H2SO4, TRS yield increased
from 77.43% to 81.67% on increasing liquid to solid ratio from 10 to
30 and further increase in liquid/solid ratio decreased TRS yield to
63.23%. Similarly, using 1 M H2SO4, significant increase in the yield
of TRS was found i.e. from 79.56% to 83.67% on increasing liquid/
solid ratio from 10 to 20 and subsequently TRS yield decreased to
53.45%. Hence, optimized liquid to solid ratio is 30 for 0.75 M
concentration and 20 for 1 M concentration. It was observed that
using more than the optimised quantity of acid, reaction mixture
forms a precipitate which may be due to the regeneration of wood
[24,37]. Further, experiments were conducted using 1 M H2SO4
concentration and liquid/solid ratio of 20.
Proximate analysis
Characterstics Composition (%)
Moisture content 11.33
Ash content 6.89
Volatile matter 69.38
Fixed carbon 12.4
60 U. Tyagi et al. / Renewable Energy 146 (2020) 56e65
Fig. 2. Effect of acid to Babool wood ratio (L/S ratio) on TRS yield. (Reaction
Time ¼ 60 min, Particle size ¼
80 þ 100 mesh, IL ¼ 2g, Babool wood Loading ¼ 0.05g,
Catalyst Loading ¼ 0.05g, Temp. ¼ 393 K, RPM ¼ 500).
Table 2 summarizes the effect of pretreatment using ionic liquid
only; dilute acid only and combination of dilute acid and ionic
liquid on Babool wood. Results indicate that the synergistic effect of
[Bmim] Cl and dilute acid was found to be significant. It was
observed that TRS yield increased to 83.67% when wood was pre-
treated with dilute acid in [Bmim] Cl ionic liquid medium. It may be
due to the fact that addition of acid in [Bmim] Cl medium catalyzed
by modified activated carbon helps in breaking b- 1,4 glycosidic
bonds of cellulose network at a faster rate as [Bmim]þ ions prevent
cross linking of cellulose network and also it pairs up with oxygen
of the broken hydroxyl group. However, Cl
ions in the reaction
system easily form hydrogen bonding with hydroxyl group of cel-
lulose network that were released during acid hydrolysis and im-
proves accessibility towards breakage of b- 1, 4 glycosidic bonds
[12]. Also, modified activated carbon posses BrØnsted acidity which
forms Lewis acid assisted BrØnsted acid complex with [Bmim] Cl;
this complexation provide high acidity and catalyze the reaction at
faster rate. The induced Lewis acidity isomerises the glucose into
fructose whereas BrØnsted acid activity helps in rapid dehydration
of fructose into 5-HMF hence appropriate ration of lewis and
BrØnsted acid is essential for high yield conversion of lignocellu-
losic biomass. As a result of which maximum TRS yield was ob-
tained using a combination of [Bmim] Cl and H2SO4 catalyzed by
modified activated carbon as compared to individual effect.
3.3. Effect of hydrolysis temperature
Fig. 3 shows the effect of temperature ranging from 373 K to
473 K on Babool wood hydrolysis. Results revealed that on increase
in reaction temperature from 373 K to 393 K, approximately 4%
increase in TRS yield was observed i.e. from 79.34% to 83.67%
respectively as shown in Fig. 3. With increase in temperature, faster
disintegration of Babool wood results in increase of TRS yield. It has
Table 2
TRS yield from Babool wood at different pretreatment conditions.
S.No Pretreatment Conditions
1. Ionic Liquid [Bmim] Cl þ ACS catalyst þ Biomass
2. Biomass pretreatment with H2SO4(1 ml, 1M) þ ACS catalyst
3. Biomass pretreatment with H2SO4 (1 ml, 1M) þ IL þ ACS catalyst
*Reaction conditions: Babool wood Loading ¼ 0.05g, IL ¼ 2g, Catalyst Loading ¼ 0.05g, Reaction time ¼ 60 min, Temp. ¼ 393 K.
Fig. 3. Effect of temperature on TRS yield. (Reaction Time ¼ 60 min, Babool wood
Loading ¼ 0.05g, Particle size ¼
80 þ 100 mesh, IL ¼ 2g, Catalyst Loading ¼ 0.05g,
Liquid/Solid ratio ¼ 20, RPM ¼ 500).
been reported that reduction in crystallinity facilitates faster con-
tact with dilute acid and catalyst due to dissociation of H-ions ob-
tained from dilute acid in the reaction media [3]. Further increase in
temperature from 393 K to 473 K with an increment of 20 K grad-
ually decreased the TRS yield to 49.54%. This decrease in TRS yield
attributes to the formation of side products at high temperature.
3.4. Effect of hydrolysis time
The effect of hydrolysis time ranging 30e150 min was investi-
gated using Babool wood with particle size
80 to þ100 mesh at
393 K as shown in Fig. 4. Results indicate that TRS yield increased
from 53.21% to 70.23% with increase in reaction time from 30 min
to 60 min. Further, increase in reaction time up to 150 min,
decreased TRS yield to 49.34% due to formation of side products.
These results indicate that maximum formation of total reducing
sugar is favoured in a reaction time of 60 min and gradual decrease
in TRS yield is due to the formation of side products [42].
3.5. Effect of Babool wood loading
Fig. 5 shows the effect of Babool wood loading from 50 to
150 mg. It was observed that on increase in wood loading of
80
to þ100 mesh from 50 mg to 90 mg TRS yield increased from
83.67% to 89.32%. Further, increase in wood loading from 100 mg to
150 mg TRS yield gradually decreased to 68.54%. This may be the
result of reduction in uniform mixing of reaction mixture and hence
mass transfer resistance [22,43]. Also, high loading hinders the
interaction of ionic liquid and catalyst with Babool wood particles
and has an impinging effect on decrystallinity due to which TRS
yield decreases [23].
TRS Yield (%)
30.22
58.34
83.67
 U. Tyagi et al. / Renewable Energy 146 (2020) 56e65
3.6. Recyclability study
Recovery and reusability study of ionic liquid in hydrolysis of
lignocellulosic biomass is also important to make the process cost
effective. Recyclability study revealed that recovered ionic liquid
was successfully used till six cycles whereas after each run TRS yield
gradually decreases from 83.67% for initial run to 26.16% for sixth
run respectively. This decrease in the TRS yield was due to insuf-
ficient amount of ionic liquid that remained in the reaction system
after each cycle and hence disintegration of cellulose and hemi-
cellulose is minimised.
Fig. 4. Effect of hydrolysis time on TRS yield. (Babool wood Loading ¼ 0.05g, IL ¼ 2g,
Liquid/solid ratio ¼ 20, particle size ¼
80 þ 100, Catalyst Loading ¼ 0.05g,
Temp. ¼ 393 K, RPM ¼ 500).
Fig. 5. Effect of biomass loading on TRS yield. (Reaction Time ¼ 60 min, Particle
size ¼ .
80 þ 100 mesh, IL ¼ 2g, Catalyst Loading ¼ 0.05g, Liquid/Solid ratio ¼ 20,
Temp. ¼ 393 K, RPM ¼ 500).
61
3.7. Kinetic study
Experiments were performed to study the kinetic behaviour of
Babool hydrolysis to total reducing sugars. The rate of formation of
total reducing sugars was examined as a function of time and
temperature for H2SO4 acid concentration ranging from
(0.25e1.25 M). The first simplified irreversible series kinetic model
on biomass (Douglas Fir) for the hydrolysis of glucose in a batch
reactor was proposed by Saeman in 1945 [44]. In this study, for-
mation of total reducing sugar hydrolysed by Babool wood was
modelled using the following consecutive irreversible first order
reaction:
The reaction rate of Babool hydrolysis for the sugar formation
and further degradation can be written in the form of equation (1).
Assuming that substrate contains no sugars and decomposition
products and each stage of the reaction is irreversible first order
reaction, the above model can be described in terms of following
differential equation as;
  
S k1
¼ ðexpð
k1 tÞ
expð
k2 t (4)
S0 k2
k1
where So is the initial molar concentration of sugar (mg/L), k1 is the
rate constant for biomass hydrolysis to TRS and k2 is the rate con-
stant for sugar degradation. The value of these rate constants (k1
and k2) were evaluated using non linear regression method by
Origin Pro 8 software.
Also, dependency of rate constants over the temperature has
been described using Arrhenius equation (2);


Ea
k ¼ Aexp ð (5)
RT

Ea
lnk ¼ lnA
ð
RT (6)
where Ea is the activation energy (kJmol
1), A is the pre-
exponential factor (s
1), R is the universal gas constant (8.314
Jmol
1K
1) and T is the reaction temperature (K). The values of
parameters i.e pre-exponential factor (A) and activation energy (Ea)
have been determined using linear fitting analysis Origin Pro 8
software. All the experiments were performed in triplicate to
validate model parameters.
3.7.1. Kinetic parameters
A kinetic model applicable for acid/IL pretreated Babool wood
catalyzed by modified activated (ACS) at H2SO4 in the range of
(0.25e1.25 M) and temperature of (100e200  C) was studied. In a
typical run, 0.05 g Babool wood, 0.05 g ACS catalyst, 2 g ionic liquid,
0.5 ml of sulphuric acid was used. In Fig. 6 the experimental data
points fitted with Saeman model from literature (Saeman 1945) are
in agreement (R2 > 0.9). Table 3 summarizes the values of k1 and k2
for reducing sugar and decomposition products by fitting non
linear curve progression to the experimental values using equation
(1). In Fig. 6, it is observed that values of k1 and k2 increase with
62 U. Tyagi et al. / Renewable Energy 146 (2020) 56e65

Fig. 6. Experimental data for TRS formation and fittings to Saeman model (a) 0.25 M (b) 0.5 M (c) 0.75 M (d) 1 M (e) 1.25.
 U. Tyagi et al. / Renewable Energy 146 (2020) 56e65 63

Table 3
Kinetic parameters for formation of total reducing sugar from Babool wood using Seaman model.

Acid concentration (M) T (ºC) So (mg/L) k1 (min
1) k2 (min
1) R2

0.25 100 147.13 0.01652 0.01601 0.8832

120 190.23 0.01768 0.01661 0.97583
140 125.90 0.01362 0.01360 0.96021
160 120.63 0.01281 0.01259 0.95634
180 111.57 0.01184 0.01145 0.91899
200 102.26 0.01168 0.01120 0.86604

0.5 100 150.62 0.01662 0.01635 0.93007

120 195.03 0.01774 0.01668 0.99013
140 129.18 0.01368 0.01363 0.9803
160 124.55 0.01284 0.01260 0.9604
180 119.03 0.01194 0.01157 0.9626
200 105.73 0.01170 0.01141 0.9270

0.75 100 159.65 0.01681 0.01640 0.9471

120 202.30 0.01782 0.01672 0.9879
140 131.18 0.01370 0.01366 0.9827
160 128.59 0.01289 0.01263 0.9780
180 122.58 0.01198 0.01159 0.9860
200 110.65 0.01178 0.01148 0.9845

1 100 169.25 0.01696 0.01645 0.9533

120 210.05 0.01794 0.01680 0.9832
140 139.99 0.01381 0.01371 0.9831
160 131.02 0.01293 0.01265 0.9864
180 127.21 0.01288 0.01188 0.9865
200 119.85 0.01253 0.01173 0.9584

1.25 100 180.17 0.01713 0.01650 0.9632

120 222.30 0.01806 0.01677 0.9716
140 143.77 0.01395 0.01379 0.9776
160 136.70 0.01298 0.01270 0.9809
180 130.33 0.01290 0.01199 0.9776
200 125.23 0.01260 0.01179 0.9688

increase in acid concentration up to 60 min. The values of k1 are
higher than that of k2, which implies that production of reducing
sugars is more favoured over the formation of decomposition
products [45]. It is noteworthy that on increasing temperature from
100  C to 120  C, initial concentration of sugar (So) also increases
with increase in acid concentration from 0.25 M to 1.25 M. How-
ever, further increase in temperature from 120  C to 200  C results
in the decrease of sugar concentration due to the formation of
humins or side products. Similar observations for kinetic parame-
ters have been reported by Ref. [46].
Fig. 7 shows the experimental rate constants as a function of
temperature for acid concentration ranging from 0.25 M to 1.25 M.
Kinetic parameters Ea and A calculated are summarized in Table 4. It
was observed that on increasing temperature from 100  C to 120  C
values of k1 and k2 increase with the increase in acid concentration.
Also increase in acid concentration from 0.25 M to 1.25 M, activa-
tion energy decreased from 4.030 kJ/mol to 3.139 kJ/mol for sugar
formation and 1.301 kJ/mol to 0.963 kJ/mol for degradation prod-
ucts. The reduction in activation energy with increase in acid
concentration implies low energy is required to initiate hydrolysis
of Babool biomass in 60 min [47]. Also, decrease in activation en-
ergy with high acid concentration attributes to change in Babool
wood composition by disconstructing wood structure such as cel-
lulose and lignin depolymerization and hemicellulose

Fig. 7. Arrhenius plot for total reducing sugar and decomposition products.
64 U. Tyagi et al. / Renewable Energy 146 (2020) 56e65

Table 4
Estimated activation energy and pre-exponential factors.

Acid concentration (M) T (ºC) k1 (min
1) Ea (kJmol
1) A (min
1) k2 (min
1) Ea (kJmol
1) A (min
1)

0.25 100 0.01652 0.01625

110 0.01701 4.0300 0.0604 0.01645 1.3012 0.02472
120 0.01768 0.01661

0.5 100 0.01662 0.01635

110 0.01711 3.8728 0.0578 0.01649 1.1866 0.02395
120 0.01774 0.01640

0.75 100 0.01681

110 0.01723 3.4652 0.0512 0.01640
120 0.01782 0.01656 1.1475 0.02374
0.01672
1 100 0.01696 0.01645
110 0.01733 3.3361 0.0496 0.01659 1.0732 0.02324
120 0.01794 0.01675

1.25 100 0.01713 0.01650

110 0.01748 3.1396 0.0470 0.01688 0.96390 0.02253
120 0.01806 0.01677

decomposition. Decrease in pre-exponential factor (A) from 0.0604
s
1 to 0.047 s
1 for k1 and 0.0247 s
1 to 0.0225 s
1 for k2 implies
faster and easier degradation of sugar with increasing acid con-
centration. Literature reports that using only ionic liquid or only
mineral acid requires high activation energy to disintegrate
biomass structure [48,49]. However, synergistic effect of acid/IL
combination not only increases TRS yield but lowers activation
energy.
4. Conclusion
Combination of dilute sulphuric acid and [Bmim] Cl for pre-
treatment and subsequent hydrolysis in a single step for Babool
wood reduces the challenges associated with its structural
complexity. This method requires no delignification in a separate
step and effectively improves TRS yield. Maximum TRS yield of
83.67% was observed using particle size in the range of
80 to þ100
mesh in a reaction time of 60 min. Finally, a kinetic model was
applied to model TRS yield from Babool wood hydrolysis. A good fit
was obtained between the experimental data and the proposed
kinetic model. The developed process is cost effective and envi-
ronment friendly for conversion of forestry biomass to total
reducing sugar catalyzed by solid acid catalyst.
Acknowledgement
The authors acknowledge the financial support from Guru
Gobind Singh Indraprastha University, New Delhi, India through
FRGS Project (Faculty Research Grant Scheme: GGSIPU/DRC/FRGS/
Dr. Neeru Anand/2018/35).
Appendix A. Supplementary data
Supplementary data to this article can be found online at
https://doi.org/10.1016/j.renene.2019.06.150.
References
[1] N. Wang, J. Zhang, H. Wang, Q. Li, S. Wei, D. Wang, Effects of metal ions on the
hydrolysis of bamboo biomass in 1- butyl 3- methyl Imidazolium chloride
with dilute acid as catalyst, Bioresour. Technol. 173 (2014) 399e405. https://
doi.org/10.1016/j.biortech.2014.09.125.
[2] S. Bali, M.A. Tofanelli, R.D. Ernst, E.M. Eyring, Chromium (III) catalysts in ionic
liquids for the conversion of glucose to 5-(Hydroxymethyl) furfural (HMF):
insight into metal catalyst: ionic liquid mediated conversion of cellulosic
biomass to biofuels and chemicals, Biomass Bioenergy 42 (2012) (2012)
224e227. https://doi.org/10.1016/j.biombioe.2012.03.016.
[3] J. Cheng, N. Wang, D. Zhao, D. Qin, W. Si, Y. Tan, S. Wei, D. Wang, The
enhancement of hydrolysis of bamboo biomass in ionic liquid with chitosan e
based solid acid catalysts immobilized with metal ions, Bioresour. Technol.
220 (2016) 457e463. https://doi.org/10.1016/j.biortech.2016.08.064.
[4] A.A. Rosatella, S.P. Simeonov, R.F.M. Frade, C.A.M. Afonso, 5- Hydroxymethyl
furfural (HMF) as a building block platform: biological properties, synthesis
and synthetic applications, Green Chem. 13 (2011) 754e793, https://doi.org/
10.1039/C0GC00401D.
[5] I.J. Morales, J.S. Gonzalez, A.J. Lopez, P.M. Torres, Glucose dehydration to 5-
Hydroxymethyl furfural on zirconium containing mesoporous MCM-41 silica
catalysts, Fuel 118 (2014) 265e271. https://doi.org/10.1016/j.fuel.2013.10.
079.
[6] C. Li, B. Knierim, C. Manisseri, R. Arora, H.V. Scheller, M. Auer, K.P. Vogel,
B.A. Simmons, S. Singh, Comparison of dilute acid and ionic liquid pretreat-
ment of switch grass: biomass recalcitrance, delignification and enzyme
saccharification, Bioresour. Technol. 101 (2010) 4900e4906. https://doi.org/
10.1016/j.biortech.2009.10.066.
[7] H.W. Blanch, C.R. Wilke, Sugars and chemicals from cellulose, Rev. Chem. Eng.
1 (1982) 71e119. https://doi.org/10.1515/revce-1983-0103.
[8] F. Liu, L. Wang, Q. Sun, L. Zhu, X. Meng, F.S. Xiao, Transesterification catalysed
by ionic liquids on super hydrophobic mesoporous polymers: heterogeneous
catalysts that are faster homogeneous catalysts, J. Am. Chem. Soc. 134 (2012)
16948e16950. https://doi.org/10.1021/ja307455w.
[9] B.J. Cox, J.G. Ekerdt, Pretreatment of yellow pine in an acidic ionic liquid:
extraction of hemicellulose and lignin to facilitate enzymatic digestion, Bio-
resour. Technol. 134 (2013) 59e65. https://doi.org/10.1016/j.biortech.2013.
01.081.
[10] T.H. Hsu, G.L. Guo, W.H. Chen, W.S. Hwang, Effect of dilute acid pretreatment
of rice straw on structural properties and enzymatic hydrolysis, Bioresour.
Technol. 101 (2010) 4907e4913. https://doi.org/10.1016/j.biortech.2009.10.
009.
[11] S.S. Hassan, G.A. Williams, A.K. Jaiswal, Emerging technologies for the pre-
treatment of lignocellulosic biomass, Bioresour. Technol. 262 (2018) 310e318.
https://doi.org/10.1016/j.biortech.2018.04.099.
[12] S. Kassaye, K.K. Pant, S. Jain, Hydrolysis of cellulosic bamboo biomass into
reducing sugars via combined alkaline solution and ionic liquid pretreatment
steps, Renew. Ener. 104 (2017) 177e184. https://doi.org/10.1016/j.renene.
2016.12.033.
[13] M. Hashmi, Q. Sun, J.T.W. Tao, A.A. Shah, N. Labbe, A.J. Ragauskas, Comparison
of auto hydrolysis and ionic liquid 1-butyl-3-methylimidazolium acetate
pretreatment to enhance enzymatic hydrolysis of sugarcane bagasse, Bio-
resour. Technol. 224 (2017) 714e720. https://doi.org/10.1016/j.biortech.2016.
10.089.
[14] C. Li, Z.K. Zhao, Efficient acid catalyzed hydrolysis of cellulose in ionic liquid,
Adv. Synth. Catal. 349 (2007) 1847e1850. https://doi.org/10.1002/adsc.
200700259.
[15] R. Rinaldi, R. Palkovits, F. Schuth, Depolymerisation of cellulose using acid
solid catalysts in ionic liquid, Angrew. Chem. Int. Ed. 47 (2008) 8047e8050.
https://doi.org/10.1002/ange.200802879.
[16] C. Sievars, M.B. Valenzuela e Olarte, T. Marzialetti, I. Musin, P.K. Agrawal,
C.W. Jones, Ionic-Liquid-Phase hydrolysis of pinewood, Ind. Eng. Chem. Res.
48 (2009) 1277e1286. https://doi.org/10.1021/ie801174x.
[17] L. Vanoye, M. Fanselow, J.D. Holbrey, M.P. Atkins, K.R. Seddon, Kinetic model
for the hydrolysis of lignocellulosic biomass in the ionic liquid 1-ethyl-3-
 U. Tyagi et al. / Renewable Energy 146 (2020) 56e65
methyl-imidazolium chloride, Green Chem. 11 (2009) 390e396. https://doi.
org/10.1039/B817882H.
[18] A.M. Da Costa Lopes, K.G. Joao, D.F. Rubik, E. Bogel-Lukasik, L.C. Duarte,
J. Andreaus, R. Bogel-Lukasik, pre-treatment of lignocellulosic biomass using
ionic liquids: wheat straw fractionation, Bioresour. Technol. 142 (2013)
198e208. https://doi.org/10.1016/j.biortech.2013.05.032.
[19] P. Weerachanchai, J.M. Lee, Effect of organic solvent in ionic liquid on biomass
pretreatment, ACS Sustain. Chem Eng. 1 (2013) 894e902. https://doi.org/10.
1021/sc300147f.
[20] L.T. Trinh, Y.J. Lee, J.W. Lee, H.J. Lee, Characterization of ionic liquid pre-
treatment and the bioconversion of pretreated mixed softwood biomass,
Biomass Bioenergy 81 (2015) 1e8. https://doi.org/10.1016/j.biombioe.2015.
05.005.
[21] I. Romero, E. Ruiz, E. Castro, M. Moya, Acid hydrolysis of olive tree biomass,
Chem. Eng. Res. Des. 8 (2010) 633e640. https://doi.org/10.1016/j.cherd.2009.
10.007.
[22] A.M.J. Kootstra, H.H. Beeftink, E.L. Scott, J.P.M. Sanders, Comparison of dilute
and organic acid pretreatment for enzymatic hydrolysis of wheat straw,
Biochem. Eng. J. 46 (2009b) 126e131. https://doi.org/10.1016/j.bej.2009.04.
020.
[23] H.T. Tan, K.T. Lee, A.R. Mohamed, Pretreatment of lignocellulosic palm
biomass using a solvent e ionic liquid [Bmim]Cl for glucose recovery : an
optimisation study using response surface methodology, Carbohydr. Polym.
83 (2011) 1862e1868. https://doi.org/10.1016/j.carbpol.2010.10.052.
[24] Y.P. Wijaya, R.D.D. Putra, V.T. Widyaya, J.M. Ha, D.J. Suh, C.S. Kim, Comparative
study on two step concentrated acid hydrolysis for the extraction of sugars
from lignocellulosic biomass, Bioresour. Technol. 164 (2014) 221e231.
https://doi.org/10.1016/j.biortech.2014.04.084.
[25] G. Wang, S. Zhang, W. Xu, W. Qi, Y. Yan, Q. Xu, Efficient saccharification by
pretreatment of bagasse pith with ionic liquid and acid solutions simulta-
neously, Energy Convers. Manag. 89 (2015) 120e126. https://doi.org/10.1016/
j.enconman.2014.09.029.
[26] C. Li, Q. Wang, Z.K. Zhao, Acid in ionic liquid: an efficient system for hydrolysis
of lignocellulose, Green Chem. 10 (2008) 177e182, https://doi.org/10.1039/
B711512A.
[27] F. Parveen, T. Patra, S. Upadhyayula, Hydrolysis of microcrystalline cellulose
using functionalized Bronsted acidic ionic liquids e a comparative study,
Carbohydr. Polym. 135 (2016) 280e284. https://doi.org/10.1016/j.carbpol.
2015.08.039.
[28] U. Tyagi, N. Anand, D. Kumar, Synergistic effect of modified activated carbon
and ionic liquid in the conversion of microcrystalline cellulose to 5-
Hydroxymethyl Furfural, Bioresour. Technol. 267 (2018) 326e332. https://
doi.org/10.1016/j.biortech.2018.07.035.
[29] Y. Ansanay, P. Kolar, R.S. Shivappa, J. Cheng, S. Park, C. Arellano, Biomass
hydrolysis into sugars via activated carbon-supported sulfonic acid, Agric.
Eng. Int.: CIGR J. 18 (2016) 252e261. https://doi.org/10.1016/j.aei.2016.3938.
[30] T.222 om-02, T.204 cm-97, T.203 cm-99, Standard procedure for the esti-
mation of lignin, cellulose and hemicellulose and Extractives. http://www.
tappi.org. https://www.tappi.org/content/SARG/T222.pdf (accessed on
August 2011).
[31] S. Naik, V.V. Goud, P.K. Rout, K. Jacobson, A.K. Dalai, Characterization of Ca-
nadian biomass for alternative renewable biofuel, Renew. Energ. 35 (2010)
1624e1631. https://doi.org/10.1016/j.renene.2009.08.033.
[32] ASTM E1756-01 and T 412 om-02, Laboratory Analytical Procedure for esti-
mation of proximate analysis and total solids, Technical Report NREL/TP-510-
42621-22 January 2008, https://www.nrel.gov/docs/gen/fy08/42621.pdf.
[33] G.L. Miller, Use of Di-nitro salicylic acid reagent for determination of reducing
sugar, Anal. Chem. 31 (1959) 426e428. https://pubs.acs.org/doi/pdf/10.1021/
ac60147a030.
65
[34] R. Garg, N. Anand, D. Kumar, Pyrolysis of Babool seeds (Acacia Nilotica) in a
fixed bed reactor and bio-oil characterization, Renew. Energ. 96 (2016)
167e171. https://doi.org/10.1016/j.renene.2016.04.059.
[35] M. Haneef, L. Ceseracciu, C. Canale, I.S. Bayer, J.A. Guerrero, A. Athanassiou,
Advanced materials from fungal mycelium: fabrication and tuning of physical
properties, Sci. Rep. 7 (2017) 1e11. https://doi.org/10.1038/srep41292.
[36] P. Mohanty, S. Nanda, K.K. Pant, S. Naik, J.A. Kozinski, A.K. Dalai, Evaluation of
the physiochemical development of biochars obtained from pyrolysis of
wheat straw, timothy grass and pinewood: effects of heating rate, J. Anal.Appl.
Pyrolysis 104 (2013) 485e493. https://doi.org/10.1016/j.jaap.2013.05.022.
[37] R. Timung, N.N. Deshavath, V.V. Goud, V. Dasu, Effect of subsequent dilute acid
and enzymatic hydrolysis on reducing sugar production from sugarcane
bagasse and spent citronella biomass, J. Ener. 14 (2016) 1e12. https://doi.org/
10.1155/2016/8506214.
[38] N. Mosier, R. Hendrickson, N. Ho, M. Sedlak, M.R. Ladisch, Optimization of pH
controlled liquid hot water pretreatment of corn strove, Bioresour. Technol.
96 (2005a) 1986e1993. https://doi.org/10.1016/j.biortech.2005.01.013.
[39] A.T.W.M. Hendriks, G. Zeeman, Pretreatment to enhance the digestibility of
lignocellulosic biomass, Bioresour. Technol. 100 (2009) 10e18. https://doi.
org/10.1016/j.biortech.2008.05.027.
[40] N. Mosier, C. Wyman, B. Dale, R. Elander, Y.Y. Lee, M. Holtzapple, M. Ladisch,
Features of promising technologies for pretreatment of lignocellulosic
biomass, Bioresour. Technol. 96 (2005b) 673e686. https://doi.org/10.1016/j.
biortech.2004.06.025.
[41] J.J. Hernandez, G.A. Almansa, A. Bula, Gasification of biomass wastes in an
entrained flow gasifier: effect of the particle size and the residence time, Fuel
Process. Technol. 91 (2010) 681e692, in: https://doi.org/10.1016/j.fuproc.
2010.01.018.
[42] B.V. Babu, A.S. Chaurasia, Heat transfer and kinetics in the pyrolysis of
shrinking biomass particle, Chem. Eng. Sci. 59 (2004) 1999e2012. https://doi.
org/10.1016/j.ces.2004.01.050.
[43] A.M.J. Kootstra, N.S. Mosier, E.L. Scott, H.H. Beeftink, J.P.M. Sanders, Differ-
ential effects of mineral and organic acids on the kinetics of arbinose degra-
dation under lignocellulosic pretreatment conditions, Biochem. Eng. J. 43
(2009a) 92e97. https://doi.org/10.1016/j.bej.2008.09.004.
[44] J.F. Saeman, Kinetics of wood saccharification-hydrolysis of cellulose and
decomposition of sugars in dilute acid at high temperature, Ind. Eng. Chem. 37
(1945) 43e52. https://pubs.acs.org/doi/pdf/10.1021/ie50421a009.
[45] S.X. Chin, C.H. Chia, Z. Fang, S. Zakaria, X.K. Li, F. Zhang, A kinetic study on acid
hydrolysis of oil palm empty fruit bunch fibers using a microwave reactor
system, Energy Fuels 28 (2014) 2589e2597. https://doi.org/10.1021/
ef402468z.
[46] V.D. Lacerda, B.L. Sotelo, A.C. Guimaraes, S.H. Navarro, M.S. Bascones,
L.M. Gracia, P.M. Ramos, E.P. Lebena, J.M. Gil, A kinetic study on microwave
assisted conversion of cellulose and lignocellulosic waste into hydrox-
ymethylfurfural/furfural, Bioresour. Technol. 180 (2015) 88e96. https://doi.
org/10.1016/j.biortech.2014.12.089.
[47] G. Zhu, X. Zhu, Q. Fan, X. Wan, Production of reducing sugars from bean dregs
waste by hydrolysis in subcritical water, J. Anal. Appl. Pyrolysis 90 (2011)
182e186. https://doi.org/10.1016/j.jaap.2010.12.006.
[48] Z.P. Zhao, X.L. Wang, G.Y. Zhou, Y. Cao, P. Lu, W.F. Liu, Hydrolysis kinetics of
inulin by imidazole-based acidic ionic liquid in aqueous media and bioethanol
fermentation, Chem. Eng. Sci. 151 (2016) 16e24. https://doi.org/10.1016/j.ces.
2016.05.017.
[49] A.S. Khan, Z. Man, M.A. Bustam, C.F. Kait, Z. Ullah, A. Nasrullah, M.I. Khan,
G. Gonfa, P. Ahmad, N. Muhammad, Kinetics and thermodynamic parameters
of ionic liquid pretreated rubber wood biomass, J. Mol. Liq. 223 (2016)
754e762. https://doi.org/10.1016/j.molliq.2016.09.012.