Waste and Biomass Valorization

https://doi.org/10.1007/s12649-019-00866-9

ORIGINAL PAPER

Effects of Acetic Acid Pretreatment and Pyrolysis Temperatures

on Product Recovery from Fijian Sugarcane Bagasse
Viliame Savou1 · Shogo Kumagai1   · Yuko Saito1 · Tomohito Kameda1 · Toshiaki Yoshioka1

Received: 8 April 2019 / Accepted: 21 October 2019

© Springer Nature B.V. 2019

Abstract
The utilization and storage of surplus waste bagasse in underdeveloped sugar mills is problematic due to limited space within
the sugar factories and pollution from bagasse debris, thus, pyrolysis offers a possible solution for the clearance of factory
bagasse wastes. In this study, Fijian sugarcane bagasse was subjected to pyrolysis, and the effects of combined acetic acid
­(CH3COOH) pretreatment and high temperature on the distribution of gaseous products were investigated. Bagasse wastes
delivered from Fiji were pretreated with different concentrations of ­CH3COOH (1, 3, 6, and 9 mol L−1 (M)) to partially
hydrolyze cellulose, hemicellulose, and lignin. The pretreatment disrupted the bagasse cell structures and enhanced bagasse
pyrolysis. The gas yield from untreated bagasse at 500 °C (117.7 mL g−1) significantly increased (350.4 mL g−1) with the
combination of 1 M ­CH3COOH pretreatment and thermal cracking at 800 °C. This study will aid the recovery of energy or
chemical feedstock from surplus Fijian bagasse, which cannot be otherwise used effectively.
Graphic Abstract

bagasse
lignin
acid pyrolysis
pretreatment 500 °C 500 / 800 °C gas
pyrolysates
tars
char
hemicellulose
cellulose

Keywords  Biomass pyrolysis · Bagasse · XPS · Acid pretreatment · Hydrolysis · Thermal cracking

Statement of Novelty pretreatment is essential for the cleavage of long chain

The pyrolysis of biomass/sugarcane bagasse has been widely
investigated by many researchers. This work reports effects
of the combination of acid pretreatment and elevated tem-
perature on the pyrolysis of sugarcane bagasse. The acid
Electronic supplementary material  The online version of this
article (https​://doi.org/10.1007/s1264​9-019-00866​-9) contains
supplementary material, which is available to authorized users.
* Shogo Kumagai
kumagai@tohoku.ac.jp
1
Graduate School of Environmental Studies, Tohoku
University, 6‑6‑07 Aoba, Aramaki‑aza, Aoba‑ku, Sendai,
Miyagi 980‑8579, Japan
lengths of cellulose and hemicellulose in bagasse, so they
are easier to pyrolyze. The use of high temperature is to
enhance the gaseous production by the thermal cracking
of pyrolysis tars. The tube reactor pyrolysis in this work
has two chambers, the pyrolysis chamber heated at 500 °C,
which produces volatiles that enter into the second chamber.
The temperature of the second chamber is being altered in
this work comparing the pyrolysis of pyrolysates at 500 and
800 °C respectively.
From this study we conclude that acid pretreatment of
bagasse and increased temperature favours the chemical
recovery process. This data is useful when determining eco-
nomically feasible and cost effective methods of converting

13
Vol.:(0123456789)

Fiji’s excess sugarcane bagasse wastes into feedstock for
biofuel production.
Introduction
Biomass is made up of large lignocellulosic molecules that
determine its physical and chemical properties and thus the
calorific value of each type of biomass. The bonds between
adjacent C, H, and O molecules of organic matter can be
broken down by digestion, combustion, and decomposition
to harvest the stored chemical energy. Biomass is abundant
in tropical regions, especially in developing countries that
depend on agriculture. Its usage offers an economic and
technical solution for generating value-added products such
as fuels and chemicals [1–5].
Sugarcane is the main raw material used in sugar and
ethanol industries. Developing countries host three-quarters
of the global sugar industry [6], which has also played an
important role in the Fijian economy since 1872. Bagasse
is the dry material that remains after the crushing of sugar-
cane for sugar production. Bagasse has been widely used
for the production of energy, such as electricity and heat
[7, 8], bioethanol [8–10], pellets [3, 11, 12] charcoal [13],
and biochemicals, such as furfural [14, 15], xylitol [16,
17], enzymes [18], vanillin, and biopolymers. Mixtures of
bagasse and wood chips are currently being used to gener-
ate heat and power for the three Fijian sugar mills, with the
surplus energy outsourced as electricity to the Fiji Electricity
Authority grid via cogeneration [8]. However, each crushing
season produces excess bagasse, which has other uses, such
as feedstock in biofuel production. The increasing demand
for sugar has led to an increased production of bagasse.
However, these residues are often mismanaged which causes
various types of air and land pollution, especially in mills,
where basic process technology is used.
The major constituents of bagasse are lignocellulosic
components, namely cellulose, hemicellulose, and lignin.
Pyrolysis enables the conversion of lignocellulosic matter
of surplus, unused sugarcane bagasse into a wider range
of products that can be used as fuel and feedstock for fuel
production. The pyrolysis of sugarcane bagasse has been
extensively investigated. Garcia-Perez et al. [19] provided
a background study on the vacuum pyrolysis of sugarcane
bagasse, and the produced bio-oil was a viable liquid fuel
with low ash content, low viscosity, high calorific value, and
low content of insoluble methanol materials.
Acid pretreatment is essential for the hydrolysis of
the lignocellulosic molecules of the bagasse into shorter
chains, which are easier to pyrolyze. The effect of acid
washing on the pyrolysis conversion of bagasse into sug-
ars, especially levoglucosan, has been investigated using
0.1 wt% ­HNO3 with the addition of 0.1–0.3 wt% ­H2SO4
13
Waste and Biomass Valorization
[20]. Acid washing with the addition of 0.2 wt% ­H2SO4
and a pyrolysis temperature of 350 °C yielded the great-
est amount of levoglucosan. Similarly, Jiang et al. [21]
recorded increased levoglucosan from the pyrolysis of
sugarcane bagasse and corn cob hydrolyzed by diluted
­H2SO4, which was confirmed by Kumagai et al. [22] in
the pyrolysis of Japanese cedar wood. Similarly, we con-
firmed the effects of ­H2SO4 pretreatment on the pyrolysis
of Fijian sugarcane bagasse, which resulted in enhanced
oil production and higher gas yields [23]. Oudenhoven
et al. [24] demonstrated the removal of alkali and alkali
earth metals by acid pretreatment, which catalyze biomass
decomposition by reducing the volatile yields, and char-
forming reaction [25, 26].
We selected acetic acid ­(CH3COOH), as an easily avail-
able and inexpensive organic acid in Fiji, for acid pretreat-
ment. Acetic acid pretreatment incurs lesser degradation
of products compared to ­H2SO4 [27] and after use it can
easily be burnt, used for fertilizing soils, or applied for
the enrichment of animal feed [28]. Previous publications
have reported the effects of H­ 2SO4 (1, 3, 6 and 9 M) pre-
treatment on the pyrolysis products [22, 23], therefore, in
this study similar concentrations were investigated using
organic acetic acid solution for comparison. The obtained
pyrolysis oil and gas were feedstock for chemicals or
energy sources with higher calorific values than original
sugarcane bagasse. Since we have already reported on the
effects of acid pretreatment on the distribution of tar prod-
ucts [23], we focused on the effects of acid pretreatment
on the recovery of gaseous products in this study. The
bagasse was pretreated with different concentrations of
­CH3COOH, and the pretreated bagasse was characterized.
The pretreated bagasse was pyrolyzed at 500 °C, and the
pyrolysates were further pyrolyzed at 500 or 800 °C to
reveal the combined effects of C ­ H3COOH pretreatment
and pyrolysis temperature on characteristics of Fijian
bagasse pyrolysis.
Materials and Methods
Materials
The Fiji Sugar Corporation, the only sugar processing body
in Fiji, provided the bagasse samples for this study. These
samples were oven-dried at 105 °C for 48 h to reduce the
moisture content, ground using a metallic blender, and
separated via sieving to particle sizes of less than 125 µm.
Proximate, ultimate, and component analyses on the origi-
nal samples were conducted (Table 1), following previously
published procedures [29]. The detailed procedure is sum-
marized in the supplementary material.
Waste and Biomass Valorization

Table 1  Ultimate, proximate, Untreated 1 M ­CH3COOH 3 M ­CH3COOH 6 M ­CH3COOH 9 M ­CH3COOH
and compositional analyses
of untreated and C
­ H3COOH- Ultimate analysis
pretreated sugarcane bagasse
 C (%) 42.7 44.5 43.6 43.9 37.5
 H (%) 5.9 5.9 5.5 5.6 5.0
 O (%)a 50.7 49.0 50.2 49.7 57.0
 N (%) 0.6 0.6 0.6 0.7 0.5
 S (%)  + b 0.1 0.1 0.1  + 
Proximate analysis
 Moisture (%) 4.8 3.1 4.0 3.9 2.6
 Volatile matter (%) 68.1 71.7 71.4 71.0 70.4
 Ash (%) 16.3 15.4 11.4 11.3 11.7
 Fixed carbon (%) 10.8 9.8 13.2 13.8 15.3
Component analysis
 Hemicellulose (%) 28.9 22.5 23.6 21.2 20.9
 Cellulose (%)a 32.6 42.3 41.5 39.2 40.9
 Lignin (%) 9.2 10.6 13.8 14.4 14.5
 Extractives (%) 14.4 9.2 9.8 13.8 11.9
 XPS analysis
 O/C 0.69 0.66 0.56 0.47 0.45
a
 Calculated by weight difference; b Quantity less than 0.05

Pretreatment of Sugarcane Bagasse with ­CH3COOH
Solution
Solutions (100 mL each) of various ­CH3COOH concentra-
tions (1, 3, 6, and 9 M) were prepared, and 1 g of the sieved
bagasse samples was added to each solution. The solution
was agitated at ambient temperature for 1 h using a mag-
netic stirrer at 700 rpm. After agitation, the solution was
filtered and washed continuously with deionized water until
a neutral pH was achieved. The filtered residues were oven-
dried at 105 °C for 24 h. After drying, the pretreated bagasse
samples were allowed to cool down in desiccators before the
samples were weighed to determine the weight loss.
Characterization of Original and Pretreated Bagasse
Ultimate, proximate, and component analyses of the
­CH3COOH-pretreated bagasse samples were conducted fol-
lowing the procedure explained in the supplementary mate-
rial. The weight loss of untreated and pretreated bagasse
samples during pyrolysis was investigated using a thermo-
gravimetric analyzer (Seiko Instruments, Tokyo, Japan,
TG/DTA6200). ­N2 gas (flow rate: 80 mL min−1) was used
to quench the inner furnace after adding 5 mg of sample.
Samples were decomposed in the thermogravimetric ana-
lyzer under temperatures of 50–900 °C at a heating rate of
10 °C min−1. The measurements were controlled by Muse
4.1 software (Seiko Instruments).
X-ray photoelectron spectroscopy (XPS; Axis Ultra,
Shimadzu Corporation, Kyoto, Japan) measurements
were used to study the surface chemistry of untreated and
­CH3COOH-pretreated sugarcane bagasse using a Mg Kα
line. XPS spectra were processed and analyzed using
CasaXPS 2.3.18 software. The XPS spectra of carbon C 1s
excitation were calibrated at a binding energy of 284.6 eV.
The morphological changes resulting from acid pretreatment
were observed by scanning electron microscope (Miniscope,
Hitachi High Technologies, Tokyo, Japan, S-4800).
Pyrolysis Experiments
Pyrolysis experiments were performed in a two-stage quartz
tube reactor heated by an electric furnace [30]. The first
stage comprised bagasse pyrolysis at 500 °C, since the main
pyrolysis reaction of bagasse is almost completed at this
temperature (Fig. 1) [23]. Briefly, a sample holder contain-
ing bagasse (0.3 g, untreated or acid-pretreated) was placed
on top of the reactor and He gas was introduced at a flow
rate of 150 mL min−1. Once the He gas had stabilized, the
first reactor was heated to 500 °C, and the second reactor to
500 or 800 °C. After the desired temperatures were reached,
the sample was carefully lowered into the first reactor. The
volatiles from the first stage were directly passed into the
second stage.
The second stage temperature was investigated at both
500 and 800 °C for each sample. Pyrolysis in the first reac-
tor occurred for 20 min, which was sufficient for the main
pyrolysis reaction to be completed (Fig. 1) [23]. Two cool-
ing traps were used to gather the liquid tars: volatiles were
first cooled by ice, and the uncondensed volatiles were then

13

100 0.3
Untreated
1 M CH3COOH
75 3 M CH3COOH
TG
6 M CH3COOH 0.2
DTG [min-1]
TG [wt%]
9 M CH3COOH
50
0.1
25
DTG
0.0
0
0 100 300 500 700 900
Temperature [ºC]
Fig. 1  TG and DTG curves of untreated bagasse, and 1, 3, 6, and 9 M
­CH3COOH-pretreated bagasse
cooled by liquid N. The remaining uncondensed volatiles
were collected as gaseous products in an aluminum gas bag.
At the end of the reaction, the cooling traps were defrosted
in a water bath. The He gas flow was maintained for a further
20 min to transfer uncondensed gases, such as C ­ O2 and ­CH4,
into the gas bag, which was later analyzed by gas chroma-
tography (GC). The sample holder containing primary char
was weighed, but the secondary char deposited on the reac-
tor wall was not quantified as they were not dissolved in the
tetrahydrofuran (THF) solution used to collect tars products.
The condensers were weighted before and after the pyrolysis
reaction to quantify the liquid tar products. The products
were defined as follows: (1) gases collected in the aluminum
gas bag (2) tars collected in the cooling traps, and (3) char
that remained in the sample holder. Pyrolysis experiments
were done in triplicate for each experimental condition to
confirm the reliability of the results.
Product Analysis Methods
Gas products were identified by GC–mass spectrom-
etry (GC–MS) via a gas chromatograph (Agilent-6890 N)
equipped with a mass-selective detector (5975C) and a CP-
PORABOND Q column. Gases were quantified using a GC-
flame ionization detector (GL Science Inc., Tokyo, Japan;
GC4000 column: CP-PORABOND Q) and GC-thermal con-
ductivity detector (GL Science Inc.; GC323 column: active
C 30–60 mesh size) by calibration against standard gases.
Tar products were collected from the reactor and condensers
using THF solution and identified by GC–MS (GC: HP6890;
MS: HP5975; column: inertCap 5MS/Sil) provided by Hewl-
ett-Packard Japan Ltd. The yields of pyrolysis tars and char
were determined by the weight differences of the condensers
and sample holders, respectively, before and after pyrolysis.
The products were standardized based on the weight of the
input sample.
13
Waste and Biomass Valorization
Results and Discussion
Characterization of Acid‑Pretreated Sugarcane
Bagasse
The results of the proximate and ultimate analyses of
untreated and C ­ H 3COOH-pretreated bagasse are sum-
marized in Table 1. The variation in elemental analyses
of the bagasse before and after acid pretreatment, except
for the 9 M ­CH3COOH pretreatment, was almost negli-
gible. The O content in the 9 M ­C H 3COOH pretreated
bagasse was greatly increased, which may be unfavorable
for pyrolysis due to its combustion behavior and charac-
teristics. Hemicellulose content slightly decreased with
increasing ­CH3COOH concentration due to the enhanced
solubility of hemicellulose by acid hydrolysis [31]. The
cellulose content was the highest in the 1 M ­CH3COOH
pretreatment and decreased with increasing ­C H 3COOH
concentration. Lignin content increased with increas-
ing the ­CH3COOH concentration. The volatile matter of
bagasse also increased with increasing acid concentration,
suggesting that C ­ H3COOH pretreatment increased cleav-
age of cellulose, hemicellulose and lignin into smaller
molecules, which enhanced pyrolysis. Acid pretreatment
influences the removal of alkali and alkali earth metals
that inhibit the volatility of the biomass samples [32, 33].
Thus, the volatile content of acid-pretreated bagasse was
higher than that of the raw sample. In fact, Na (0.7 wt%),
K (1.2 wt%), Ca (0.1 wt%), and Mg (0.1 wt%) contents in
the untreated samples were respectively reduced to 0.3,
0.5, 0.02, and 0.01 wt% in 9 M C ­ H3COOH-pretreated sam-
ples. The reduction in alkali and alkali earth metals also
results in the reduction of ash content after acid pretreat-
ment [34, 35].
Cellulose, hemicellulose, and lignin are the main compo-
nents of biomass, and their thermal decomposition processes
in bagasse are illustrated in the DTG curves in Fig. 1. For
untreated sugarcane bagasse, two maximum peaks occurred
at 286 and 345 °C, which bear shoulders attributed to hemi-
cellulose and cellulose, respectively. Hemicellulose consists
of various saccharides, including xylose, mannose, glucose,
and galactose, has no definite structure, and has numerous
branches [36] that easily degrade into volatiles (e.g., CO and
­CO2) at low temperatures. On the other hand, cellulose com-
prises polymers of glucopyranose residues linked by β-1,4-
glycosidic bonds [37], which accounts for their decomposi-
tion at a higher temperature than hemicellulose. Lignin is
made up of aromatic rings with numerous branches, with
a wide reactivity range, which allows decomposition in an
equally wide temperature range (100–900 °C).
With acid pretreatment, the maximum peaks for hemi-
cellulose decreased, and cellulose maximum peaks shifted
Waste and Biomass Valorization
to lower temperatures. Hemicellulose is more soluble in
water than cellulose is [38], and it is therefore more easily
hydrolyzed by acid pretreatment. The smaller, branched
hemicellulose structure is more easily broken than that
of longer, unbranched cellulose. This hemicellulose peak
reduction with increasing acetic acid concentration corre-
lated with the decreased hemicellulose content (Table 1).
The maximum peak for the cellulose shoulder of untreated
bagasse appeared at 367 °C, but with increasing acid pre-
treatment, the shoulder appeared at lower temperatures, for
instance, at 344 °C for 9 M ­CH3COOH pretreated bagasse.
The diluted acid hydrolysis of cellulose requires higher
temperatures and longer residence times [31], which were
not adhered to during ­C H 3COOH pretreatment in this
study. Therefore, the left shift of DTG cellulose maximum
peaks could be due to the loosening of the cellulose struc-
ture after acid pretreatment, allowing pyrolysis at lower
temperatures. The obtained results suggest that acid pre-
treatment enhanced the partial hydrolysis of the cellulose
and hemicellulose, without changing the overall structural
make-up of the bagasse, as the ultimate analysis of the acid
pretreated bagasse (Table 1) did not change significantly.
XPS spectra of the bagasse samples, corresponding to
C1s and O1s spectra are, summarized in Fig. 2. The O/C
atomic ratio calculated by using the peak areas of C1s and
O1s (Figure S1) is summarized in Table 1. After acid pre-
treatment, the C content on the bagasse surface increased,
whereas the O content decreased, causing a decreased O/C
ratio. This decrease in O/C ratio from 0.69 for untreated to
0.45 for 9 M C ­ H3COOH-pretreated bagasse indicated the
high lignin proportions on the bagasse surface after pretreat-
ment and the corresponding reduction in hemicellulose and
cellulose contents. This supports the compositional analysis
and TG/DTG data presented in Table 1 and Fig. 1, respec-
tively. Previous studies have reported the degradation of cel-
lulose and polymers in biomass by detecting the O/C ratio
[39, 40]. The theoretical O/C ratio of cellulose C­ 6H10O5 is
0.83, and that of hemicellulose ­C5H8O4 is 0.8. The lignin
structure is more complex and difficult to calculate, having
an O/C ratio ranging from 0.25 to 0.40 [41, 42].
The chemical structures of the surfaces of acid-pre-
treated bagasse were evaluated using C 1s and O 1s spec-
tra. The deconvoluted peaks of C 1s and O 1s of untreated
and acid-pretreated sugarcane bagasse are shown in Fig. 2a
and b, respectively. Four peaks are visible from the XPS
spectrum of the C1s peak expressed as C ­ 1–C4, and these
C bands correspond to C–C and/or C–H ­(C1), C–OH ­(C2),
C=O and/or O–C–O ­(C3), and O=C–O ­(C4), respectively.
The binding energies obtained in this study agreed with
published values for biomass materials [39, 43, 44]. Fig-
ure 2c summarizes the variation in peak area intensities
of specific C-bonds ­(C1–C4) after the ­CH3COOH pretreat-
ment. ­C1 is usually associated with C linked to C groups
(C–C) present in lignin, cellulose, hemicellulose, and
extractives, whereas ­C 2 mainly originated from C–OH
linkages from cellulose and hemicellulose [39, 45]. The
peak area of ­C 1 increased from 65.1 to 73.8%, whereas
that of ­C2 decreased from 24.8 to 19.9% for untreated and
3 M ­CH3COOH-pretreated bagasse, respectively (Fig. 2c).
The increase in the ­C1 peak area after acid pretreatment
indicated the increase of lignin ratios (Table 1). The acid
pretreatment assisted the partial hydrolysis of hemicellulose
components, and the lignin ratio consequently increased on
the surface of the bagasse. The C ­ 2 peak area, on the other
hand, decreased with increasing C ­ H3COOH concentration.
This suggests a reduction in cellulose and hemicellulose
ratios on the surface of bagasse by hydrolysis. The area per-
centage of C ­ 3 components slightly increased from 7.9 to
8.6% for untreated and 1 M ­CH3COOH-pretreated bagasse,
respectively, and then decreased with a further increase in
acid concentration. This indicated that the percentage con-
tribution of O–C–O linkages in cellulose and hemicellulose
was highest at this acid concentration in comparison with
­C1 lignin, which decreased from 65.1 to 61.6% for untreated
and 1 M C ­ H3COOH-pretreated bagasse, respectively. This
was consistent with the increased cellulose fractions from
33 to 36 wt% for untreated and 1 M ­CH3COOH-pretreated
bagasse, respectively (Table 1). ­C4 peak areas also slightly
decreased with increasing acid concentration, namely from
2.3 to 1.9% for untreated and 9 M C ­ H3COOH-pretreated
bagasse, respectively. These peaks arose from esters and lac-
tones (O–C=O) [46] in the carboxyl groups of hemicellu-
lose. Therefore, the reduction in C
­ 4 peak area supported the
decreased hemicellulose content in the bagasse (Table 1).
The O 1s spectra (Fig. 2b) were deconvoluted into three
peaks, ­n amelyO 1–O 3. The most intense peak is was O ­ 2
at 529 ± 0.3 eV, whereas ­O1 and ­O3 components had low
intensities at 527 ± 0.3 and 531 ± 0.3 eV, respectively. The
components of O and C atoms are related [43]. The O ­ 1
component is related to the ­C3 type, which is mainly attrib-
utable to the C=O bond associated with lignin. The inten-
sities of ­O1 peaks increased with increasing ­CH3COOH
concentration, which was also recognized in the increase
in peak areas from 2.6 to 6.8% for untreated and 9  M
­C H 3COOH-pretreated bagasse, respectively (Fig.  2d).
This supports the decrease in cellulose and hemicellulose
on the fiber surfaces and the increase in lignin compo-
nents. The ­O2 component is related to ­C2  as C–O bonds
associated with cellulose and hemicelluloses. ­O 2 peaks
decreased in intensity with increasing acid concentration,
which indicated a reduction in cellulose and hemicellu-
lose components on the surface of the bagasse. This was
confirmed by the composition analysis of cellulose pro-
portions in Table 2. ­O3 peaks correspond to the O=C−O
bonds in hemicellulose as ­C4 peaks. The hemicellulose
content was partially hydrolyzed by acid pretreatment.
13
 Waste and Biomass Valorization

Fig. 2  a C 1s and b O 1s
spectra of untreated and (a) (b)
­CH3COOH-pretreated samples
and relative intensity of specific
C−C/C−H C1 O2
bonds obtained from c C 1s and Untreated C-O
d O 1s spectra C−O C2 C=O/
C=O/O−C−O O-C-O
C O=C−O O3
O=C−O C4 3 O1
C1 O2

Intensity [CPS]
1 M CH 3COOH C2
C3
C4 O3 O1
C1 O2
3 M CH 3COOH
C2
C
C 3 O3 O1
4
C1 O2
6 M CH 3COOH
C2
C3 O1
C4 O3
C1 O2
9 M CH 3COOH
C2
C
C4 3 O3 O1
296 292 288 284 280 540 536 532 528 524
Binding energy [eV]

(c) (d)
100
C-O
Relative Intensity [Area %]

80 C−C/C−H
60

40
C-O
20
O=C−O C=O/ O-C-O O=C−O C=O/ O-C-O
0
U 1 3 6 9 U 1 3 6 9
CH3COOH concentration [M]

Figure 3 shows the microscope images of the untreated especially after the severe acid pretreatment (Fig. 3 (d),
and ­CH3COOH-pretreated bagasse. The untreated sugar- (e)).
cane bagasse sample had a clearly outlined cell structure. The weight loss of 15.7, 17.8, 19.0 and 25.8 wt% was
After acid pretreatment, the cell structures were disrupted, recorded for 1, 3, 6 and 9 M C
­ H3COOH respectively. Acid

13
Waste and Biomass Valorization

Table 2  Weight composition CH3COOH Conc. (M) Ub 1 3 6 9 U 1 3 6 9

of pyrolysis products from
untreated and C­ H3COOH- T2 (°C)a
500 500 500 500 500 800 800 800 800 800
pretreated bagasse
Total gas (wt%) 18.7 22.2 16.9 12.5 11.9 39.5 45.1 39.5 36.0 32.6
CO 5.2 5.2 7.8 4.4 4.7 18.1 26.6 22.0 18.5 13.9
CO2 11.4 14.4 7.5 6.4 6.2 12.2 11.6 8.9 8.0 8.0
CH4 0.7 1.1 0.6 0.8 0.4 4.3 4.2 5.8 7.1 4.5
C2H4 0.4 0.4 0.3 0.3 0.3 2.7 2.2 2.2 2.1 5.7
C2H6 0.2 0.1 0.1 0.1 0.1 0.2 0.2 0.3 0.2 0.3
C3H6 0.3 0.9 0.3 0.2 0.2 0.1 0.1 0.2 0.1 0.2
C3H8 0.1 0.1  + c 0.1  +   +   +   +   +   + 
C4H6 0.1  +   +  0.1  +  1.6  +   +   +   + 
C4H8 0.2 0.1 0.2  +   +  0.2 0.1  +   +  0.1
C4H10 0.2  +  0.1 0.1  +  0.1  +   +   +   + 
Tar (wt%) 38.4 37.5 38.3 39.8 42.7 21.5 18.8 17.9 17.1 14.8
Char (wt%) 32.9 33.9 36.6 34.9 33.0 30.1 30.6 38.7 35.6 36.8
Total (wt%) 90.1 93.6 91.8 90.2 90.4 91.0 94.4 96.2 88.6 84.3
a
 Temperature of the second reactor; bUntreated bagasse sample; cValue less than 0.05
Bold value indicates total balances

Fig. 3  Scanning electron microscope images of a untreated and b 1, c 3, d 6, and e 9 M C

­ H3COOH-pretreated bagasse

pretreatment enhances the partial hydrolysis of the lignocel-
lulosic components. This occurs by the attacking of the ether
­ + ions, causing
bonds of cellulose and hemicellulose by the H
their cleavage to form products with shorter chain lengths.
The schemes for the partial hydrolysis reactions have been
reported [22].This dilute acid pretreated bagasse containing
shorter chain lengths is more favorable to achieving higher
pyrolysis products, as reported in previous pyrolysis studies
of acid pretreated biomass [22, 47]. The higher acid con-
centrations may have influenced product degradation which
resulted in the reduced pyrolysis yields. The acid partial
hydrolysis influenced the reduction in hemicellulose content,
thus the lignin proportions were enhanced in the pretreated
samples.
Effects of Combined ­CH3COOH Pretreatment
and Pyrolysis Temperature on Pyrolysate
Distribution
The volatiles produced from the first pyrolysis chamber were
directly passed into the second chamber at temperatures of
500 and 800 °C. The obtained mass balances from bagasse
pyrolysis at the abovementioned temperatures are summa-
rized in Table 2. The unquantified fractions include second-
ary char on the reactor walls and high-molecular compounds
that could not be detected by GC analyses. GC chromato-
grams of tar for the different experimental conditions and
identification results are summarized in Figs. S2 and S3
and Tables S1 and S2, since detailed discussion on tar dis-
tribution was outside the scope of this study and has been
reported elsewhere [23].
The pyrolysis of untreated bagasse samples at 500 °C
produced yields of 18.7, 38.4, and 32.9 wt% for gas, tar, and
char, respectively. After the 1 M ­CH3COOH pretreatment,
the yields increased to 22.2, 37.5, and 33.9 wt%, respec-
tively. The effects of acid pretreatment on the composition
of gas from the pyrolysis of bagasse are shown in Fig. 4.
The total gas yield slightly increased after the 1  M
­C H 3COOH pretreatment but decreased with a further
increase in acid concentration. CO and C ­ O2 fractions made
up the majority of the gases, namely up to approximately
80–90 vol%. The main contributors of the CO and ­CO2

13

Fig. 4  Yield of gas and vol-
ume composition of gaseous
100
products obtained from the
pyrolysis of untreated and
­CH3COOH-pretreated bagasse
80
at 500 (left) and 800 °C (right)
Gas composition vol%]
60
40
20
0 0
U 1
production were cellulose and hemicellulose, respectively.
However, all three lignocellulosic components, cellulose,
hemicellulose, and lignin pyrolysis each contribute to CO
and ­CO2 production [36]. The degradation of lignin side
chains was the main contributor to ­CH4 production [48, 49].
­C2–C4 hydrocarbons resulted from the fragmentation of cel-
lulose and hemicellulose pyrolysates in the vapor phase and
side-chain degradation in lignin [50].
The resultant changes in the total CO and C ­ O2 fractions
resembled the trend of total gas yield and increased from
16 to 19 wt% for untreated and 1 M ­CH3COOH-pretreated
bagasse, respectively. The total cellulose and hemicellulose
content in the untreated and 1 M ­CH3COOH-pretreated sam-
ples were comparable (Table 1), suggesting that the slightly
enhanced production might be due to loosened cellulose
and hemicellulose. The reduction in the total CO and ­CO2
fractions with increasing ­CH3COOH concentration resulted
from the partial elimination of cellulose and hemicellulose
units by the acid pretreatment. A similar trend was observed
in our previous study using H­ 2SO4 [23]. In the pretreatment
using ­H2SO4, the 3 M concentration was optimum for pro-
ducing the highest gaseous yields of 21.2 wt%, compared
to the 1 M ­CH3COOH concentration producing 22.2 wt%
gases. ­CH3COOH is preferred acid in this study as there is
lesser degradation of products after acid pretreatment [51].
For instance, the weight loss of 20.9 and 50.3 wt% were
recorded for 6 and 9 M H ­ 2SO4 pretreated bagasse respec-
tively [23], compared to 19.0 and 25.8 wt% for 6 and 9 M
­CH3COOH pretreated bagasse. Furthermore, the removal of
alkali and alkaline earth metallic species by acid pretreat-
ment hinders the formation of CO and ­CO2 via decarboniza-
tion, decarboxylation, and de-esterification [52], resulting in
the reduction of CO and ­CO2 after acid pretreatment. ­CH4
production increased with increasing C ­ H3COOH concen-
tration as a result of the increasing lignin ratio in the acid
pretreated bagasse samples (Table1).
13
Waste and Biomass Valorization
CH
CH4
4 C2-C4
C2-C4 CO
CO CO
CO2
2 Total
Totalvolume
volume/ mL g-1
400
Total volume [mL g -1 bagasse]
300
200
100
3 6 9 U 1 3 6 9
Acid pretreatment [M]
Tar products also increased with increasing C ­ H3COOH
concentration from 38.4 to 42.7 wt% for untreated and 9 M
­CH3COOH-pretreated bagasse. This may be due to the cleav-
age of cellulose and hemicellulose ether bonds by ­H+ ions
during pretreatment, which catalyzed tar production during
pyrolysis. This trend has been observed in the pyrolysis of
­H2SO4-pretreated bagasse [23] and wood [22, 53].
Increasing the temperature of the second chamber to
800 °C increased the yield of gaseous compounds to 39.5
wt% for untreated bagasse. This was coupled with the reduc-
tion in tar components to 38.4 and 21.5 wt% for untreated
bagasse at 500 and 800 °C, respectively. The cracking of
tar components takes place at this higher temperature, and
the reduction in tar proportions by thermal cracking has
been investigated and proven in previous studies [54–56].
The highest gas yield, 45.1 wt%, was obtained from 1 M
­CH3COOH-pretreated bagasse at 800  °C (350  mL  g−1),
which was almost 2.5 times the volume of that obtained at
500 °C (139 mL g−1). At 800 °C, the C ­ O2 fractions were
reduced in the gas mix due to the influence of the Boudour-
ard equilibrium at 800 °C [57, 58].
The ­C H 4 fractions were enhanced, likely due to the
conversion of tar lignin components into gases [59]. Even
though the ­CO 2 fractions appeared lower than the cor-
responding fractions at 500 °C, the actual total yields of
both CO and C ­ O2 were greatly enhanced, e.g., from 30
and 34 mL g −1 to 62 and 84 mL g −1 for untreated and
1 M ­C H 3COOH-pretreated bagasse at 500 and 800 °C,
respectively. Light hydrocarbons were produced from
cellulose and lignin side chains. Due to the reduction in
cellulose ratio at higher acid concentrations (Table  1),
light hydrocarbons were low after acid pretreatment. The
most hydrocarbons were produced after 1 M ­CH3COOH
pretreatment. However, the increase in light hydrocarbons
at 800 °C may have resulted from the complete rearrange-
ment of the backbone of lignin oligomers in tars under
Waste and Biomass Valorization
high temperature. The char yields were comparable at
500 °C, since the first pyrolysis stage was not altered.
The acid pretreatment of Fijian sugarcane bagasse use-
fully alters the physical features and chemical composition
of the lignocellulosic structure by the hydrolysis of poly-
saccharides. Therefore, this reduces the energy demand
for various bagasse conversion processes, and also lowers
the costs associated with energy and chemical recovery
processes. The latter usage of high temperature increases
operational costs of the pyrolysis process, but can be
recovered from the high pyrolysis product yields obtained.
Conclusions
Variations in the structural properties of sugarcane bagasse
after its pretreatment with ­CH3COOH acid (1, 3, 6, and
9  M) was studied. The pyrolytic characteristics of the
pretreated bagasse were first investigated at 500 °C and
subsequently in a second pyrolysis chamber at 500 and
800 °C. The acid pretreatment of bagasse caused the par-
tial hydrolysis of hemicellulose and cellulose into shorter-
chain molecules as indicated by TG/DTG and composi-
tional analyses. XPS results supported this by indicating
reduced O/C ratios and increased C–C bonds with increas-
ing acid concentration, denoting the increased lignin pro-
portions on bagasse surfaces after acid pretreatment.
The gaseous products produced from the pyrolysis of
sugarcane bagasse increased with increasing C ­ H3COOH
concentration, from 18.7 to 22.2 wt% for untreated and
1  M ­C H 3COOH-pretreated bagasse, and enhanced by
the shorter chain-lengths that improved the volatility of
bagasse, increasing the gas yields. These values further
increased with increasing temperature to 39.5 and 45.1
wt%, respectively, along with a steep reduction in tar pro-
portions from 38.1 to 21.5 wt% for untreated bagasse at
500 and 800 °C. This was due to the thermal cracking
of tars, which contributed to the increased gas yields.
Therefore, the combined effects of shorter chain-lengths
by acid pretreatment and tar thermal cracking are essen-
tial for maximizing gas yields and reducing tars from the
pyrolysis of sugarcane bagasse.
The use of organic acids as pretreatment solvents offers
safer, more environmentally friendly disposal measures
and economical alternatives than ­H2SO4 we have reported
earlier pretreatment does. This would be a worthwhile
direction for further research for Fijian sugar mills, as it
offers an option for using surplus bagasse, while also cre-
ating possible sources of income and employment.
Acknowledgements  This work was partly supported by JSPS KAK-
ENHI (Grant Nos. 16H05893 and 19H04306).
Compliance with Ethical Standards 
Conflict of interest  The authors declare no conflict of interest.
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