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Bioethanol production from sago pith waste using microwave hydrothermal

hydrolysis accelerated by carbon dioxide

Article  in  Applied Energy · June 2014

DOI: 10.1016/j.apenergy.2014.04.076

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 Applied Energy 128 (2014) 277–283

Contents lists available at ScienceDirect

Applied Energy
journal homepage: www.elsevier.com/locate/apenergy

Bioethanol production from sago pith waste using microwave

hydrothermal hydrolysis accelerated by carbon dioxide
Saravana Kannan Thangavelu a,c, Abu Saleh Ahmed b, Farid Nasir Ani c,⇑
a
Faculty of Engineering, Computing and Science, Swinburne University of Technology, 93350 Kuching, Sarawak, Malaysia
b
Department of Mechanical and Manufacturing Engineering, Faculty of Engineering, Universiti Malaysia Sarawak, Sarawak, Malaysia
c
Faculty of Mechanical Engineering, Universiti Teknologi Malaysia, UTM 81310 Skudai, Johor D.T., Malaysia

h i g h l i g h t s

 Microwave hydrothermal hydrolysis with CO2 was carried out for SPW.
 Batch fermentation and distillation was carried out.
 GC and FTIR confirmation of distilled ethanol was done.
 Maximum of 43.8% glucose and 15.6 g ethanol per 100 g SPW was obtained.
 Lower energy consumption was observed for combined pretreatment and hydrolysis.

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

Article history: Bioethanol production from sago pith waste (SPW) using microwave hydrothermal hydrolysis acceler-
Received 16 December 2013 ated by carbon dioxide was studied. The structural change in the SPW after hydrolysis, ethanol purity
Received in revised form 5 April 2014 after fermentation, and distillation were investigated. Energy consumption for microwave hydrothermal
Accepted 23 April 2014
hydrolysis was evaluated. A maximum of 43.8% theoretical glucose and 40.5% theoretical ethanol yield
Available online 20 May 2014
were obtained. The ethanol yield coefficient obtained in fermentation was 0.47 (g ethanol per g glucose)
which was 15.6 g ethanol per 100 g dry SPW. It was also discovered that the lowest energy consumption
Keywords:
occurred when energy input was fixed at 108 kJ (900 W for 2 min), amounting to 33 kJ and 69 kJ to pro-
Microwave hydrothermal hydrolysis
Carbon dioxide
duce one gram glucose after hydrothermal hydrolysis and one gram ethanol after fermentation, respec-
Sago pith waste tively. The developed technique for SPW resulted in higher energy saving compared to previous
Bioethanol techniques in the absence of enzymes, acid or base catalyst.
Energy efficiency Ó 2014 Elsevier Ltd. All rights reserved.

1. Introduction
The research on development of renewable and sustainable
fuels is an important effort due to shortage of petrochemical fossil
fuels and environment pollution [1]. Bioethanol obtained from bio-
mass and bioenergy crops has been proclaimed as one of the feasi-
ble alternative to gasoline fuel [2]. Currently, large scale bioethanol
production is mainly from sugar containing substances and starch
grains, may not be desirable due to their feed value [3]. The ligno-
cellulosic biomass is one of the potential main sources for eco-
nomic bioethanol production globally. Agricultural, forestry (soft
and hardwoods) and industrial wastes are the major lignocellulosic
biomasses [4]. In addition, the starchy lignocellulosic biomass such
as waste from starch processing factories, potato food factories,
⇑ Corresponding author. Tel.: +60 7 5534715; fax: +60 7 5566159.
E-mail address: farid@fkm.utm.my (F.N. Ani).
beverage, and brewery factories are promising feedstock for large
scale production in tropical locations [5–9].
The sago pith waste (SPW) or sago ‘hampas’ is a fibrous starchy
lignocellulosic byproduct generated from pith of Metroxylon sagu
(sago palm) after extraction of starch [10]. In Sarawak, Malaysia
about 50–110 t of SPW are produced daily from starch processing
factories [11]. Sago pith waste (SPW) contains up to 58% starch,
23% cellulose, 9.2% hemicellulose and 4% lignin in dry basis (w/w)
which can be used as a favourable starchy lignocellulosic feedstock
for bioethanol production [12]. The bioethanol production from lig-
nocellulosic biomass involves different steps such as pretreatment,
hydrolysis, fermentation and ethanol recovery [3]. Different
pretreatments such as physical, chemical, physico-chemical and
biological have been studied in the past decade to alter structural
characteristics of lignocellulosic biomass [13]. Hydrolysis is an
essential step to produce fermentable sugars which are then
fermented into ethanol by microbial biocatalyst [4].

http://dx.doi.org/10.1016/j.apenergy.2014.04.076
0306-2619/Ó 2014 Elsevier Ltd. All rights reserved.
278 S.K. Thangavelu et al. / Applied Energy 128 (2014) 277–283
The conversion of starch, cellulose and hemicellulose into fer-
mentable sugars using energy efficient, economic and faster way
is the greatest concern for commercial fuel ethanol production.
Currently, chemical and enzyme hydrolysis are widely employed
to breakdown the starch and cellulose into fermentable sugar
[2–4]. These existing approaches tend to be slow, expensive and
of high dilutions that give poor yields of glucose [14]. Hydrother-
mal processing offers an alternative way to hydrolyze starchy
and cellulosic biomass into fermentable sugars using elevated
temperatures and pressures [15–18]. Water under hydrothermal
conditions is an attractive hydrolyzing medium because its unique
properties enable a wide variety of reactions without a catalyst
[15]. Nagamori and Funazukuri studied the glucose production
by hydrolysis of starch under hydrothermal conditions and
reported that the production of char and gaseous byproducts were
negligible [16]. Using subcritical and supercritical water at 25 MPa,
cellulose was hydrolyzed into glucose, fructose, and oligomers by
Sasaki et al. [17]. Starch hydrolysis under hydrothermal conditions
in the presence of carbon dioxide is an environmentally benign
method to produce mono and oligosaccharides because the process
does not require use of conventional acids and bases followed by
neutralization and separation [18].
Microwave heating presents a potentially faster, efficient and
selective method for thermal treatment of biomass [19]. Micro-
wave pretreatment was widely used for lignocellulosic biomass
such as Miscanthus sinensis [20], sorghum bagasse [21], sago bark
waste [22], wheat straw [23] and rape straw [24]. Fan et al. [14]
studied the microwave-enhanced formation of glucose from cellu-
losic waste through hydrothermal hydrolysis. In addition, Tsubaki
et al. [25] carried out the microwave hydrothermal hydrolysis of
cellobiose and effects of addition of halide salts. It was found that
microwave heating improved the glucose selectivity and the halide
salts improved the hydrolysis efficiency [25]. Microwave pretreat-
ment was considered as energy efficient approach for biomass
pretreatment under low pressure and temperature [19–25]. As
water is highly effective in microwave energy absorption, the com-
bination of microwaves and hydrothermal conditions accelerated
by carbon dioxide offers an interesting alternative for starchy
lignocellulosic biomass.
The objective of this research is to produce the bioethanol from
SPW using microwave hydrothermal hydrolysis accelerated by
CO2. The structural changes in the SPW after hydrolysis, ethanol
purity after fermentation, and distillation were investigated.
Finally, the energy consumption for CO2 assisted microwave
hydrothermal hydrolysis was calculated. To the best of our knowl-
edge, no comparable literature has been reported identical to this
investigation.
2. Materials and methods
2.1. Biomass preparation and chemicals
The sago pith waste (SPW) was collected from local sago starch
processing factory. It was dried by natural drying for 4 days and
oven dried at 60 °C for 6 h. Then, it was milled into less than
0.5 mm size powder using a domestic blender. The ground biomass
(moisture content of 1.2%) was stored in sealed plastic bags and
kept in the desiccator prior to use. Deionized water, dry ice (CO2)
and commercial baker’s yeast (Saccharomyces cerevisiae S288C)
were taken for experiments.
2.2. Biomass composition analysis
The chemical compositions of SPW (% of starch, cellulose, hemi-
cellulose and lignin) were analyzed using the methods described
by Noureddini and Byun [26] which was originally adopted from
National Renewable Energy Laboratory (NREL) Chemical Analysis
and Testing Laboratory Analytical Procedures # 42624 [27] and
42618 [28].
2.3. Microwave hydrothermal hydrolysis
Microwave hydrothermal hydrolysis was carried out using a
domestic microwave oven with a frequency setting of 2450 MHz.
The biomass and liquid loading ratio was fixed at 1:12 for the
experiments. Ten grams of dried SPW was submerged in 120 g of
deionized water in a 500-mL conical flask for the first run. Addi-
tionally, 10 g CO2 (dry ice) was also added for the second run.
Immediately after adding dry ice, the conical flask was closed by
rubber stopper and kept for 15 min until the dry ice is completely
dissolved. Then, the flask with loosened cap was placed at the cen-
ter of rotating circular plate in the microwave oven. Hydrothermal
hydrolysis without and with CO2 was carried out at different
microwave power rating of 550, 700 and 900 W for 1, 2, 3 and
5 min of microwave heating. The microwave hydrolysis carried
out at 700 W/3 min without CO2 and with CO2 was designated as
7MH1 and 7MH2, respectively. Moreover, the microwave hydroly-
sis carried out at 900 W/2 min without CO2 and with CO2 was des-
ignated as 9MH1 and 9MH2, respectively. Samples were taken out
to determine the concentration of glucose and byproduct such as
acetic acid, HMF and furfural by HPLC. Glucan, xylan and lignin
content after hydrolysis were also determined according to the
NREL’s analytical methods (LAP # 42618) [28].
2.4. Fermentation and distillation
The SPW hydrolysates obtained from microwave hydrothermal
hydrolysis were cooled down to room temperature. No separate
culture media were prepared for baker’s yeast (Saccharomyces cere-
visiae S288C) because baker’s yeast was directly inoculated and cul-
tured in the fermentor [9]. Six gram yeast was added to each of the
hydrolyzed samples 7MH1, 7MH2, 9HM1 and 9MH2. The fermen-
tation in conical flasks was carried out in an incubator shaker at
35 °C and 200 rpm. The pH level in the hydrolysates was noted
as 4 before fermentation without any chemical usage. Experiments
were carried out in duplicate and mean values are reported. Sam-
ples were taken out at different time intervals to determine the
concentration of ethanol produced. Furthermore, distillation was
also performed using (1000 ml BOROSIL) glass alcohol distillation
unit at 78.4 °C (boiling point of ethanol).
2.5. Glucose, by-products and ethanol analysis
The quantity of glucose, byproducts such as acetic acid, HMF
and furfural in each of the hydrolysates, and ethanol concentration
after fermentation were determined by HPLC (Agilent 1100) using
BioRad Aminex column (HPX 87H, 300  7.8) at 60 °C and 3 mM
H2SO4 as eluent at a flow rate of 0.5 mL/min with the refractive
index detector.
2.6. Fourier transform infrared (FTIR) spectroscopy analysis
The structural changes in SPW before and after microwave
hydrothermal hydrolysis with and without dry ice were analyzed
using FTIR spectroscopy. The biomass sample (5 ml) was mixed
with spectroscopic grade KBr and FTIR spectrum was recorded
between 4000 and 400 cm1 using Shimadzu spectrometer
(Shimadzu, Japan) at 1 cm1 resolution and 10 scans per sample.
Also, CAH, CAO and OAH stretching of distilled ethanol were
analyzed.
 S.K. Thangavelu et al. / Applied Energy 128 (2014) 277–283
2.7. Gas chromatography (GC) analysis
The concentration of ethanol after distillation was determined
using Gas Chromatography technique (Shimadzu, GC 2010) with
auto injector AUC 5000, ZB-624 column (Zebron), and flame ioniza-
tion detector used to find the solvent ethanol and menthol in the
solution. Oven temperature was kept constant at 140 °C along with
injector and detector at 200 °C. Nitrogen was used as a carrier
gas at 1 ml/min flow rate along with hydrogen and zero air at
30 ml/min and 300 ml/min flow rate, respectively to the detector.
2.8. Calculation
The following calculations were made to find the glucose and
ethanol yield kinetic parameters.
Glucose yield ¼ glucose obtained in hydrolysisðgÞ=initial glucose in SPWðgÞ
 100% ð1Þ
Ethanol yieldðtheoreticalÞ ¼ ethanol obtained in fermentationðgÞ
=theoretical ethanol in SPWðgÞ  100%
Ethanol yield coefficient ¼ ethanol obtained during fermentationðgÞ
=glucose in SPW hydrolysateðgÞ
Ethanol productivity ¼ ethanol obtained during fermentationðg=LÞ
=fermentation timeðhÞ
Fermentation efficiency ¼ ethanol obtained in fermentationðgÞ
=0:51  glucose in hydrolysateðgÞ  100%
Furthermore, the energy consumption during microwave
hydrothermal hydrolysis expressed by glucose yield after hydroly-
sis and ethanol yield after fermentation process were calculated
according to Eqs. (6) and (7) respectively [24].
Energy consumptionðkJ=g glucoseÞ ¼ microwave powerðkWÞ
 timeðsÞ=highest glucose in hydrolysisðgÞ
Energy consumptionðkJ=g ethanolÞ ¼ microwave powerðkWÞ
 timeðsÞ=highest ethanol during fermentationðgÞ
3. Results and discussion
3.1. Biomass composition analysis
The chemical composition analysis showed that the untreated
SPW contains 52% starch, 16% cellulose, 9.8% hemicellulose and
5.2% lignin. About 78% of SPW contains starch, cellulose and hemi-
cellulose, which are suitable for bioethanol production. These
results are comparable to Linggang et al. [12] findings. It was
assumed that all the glucose found in the biomass could be con-
verted into ethanol with a theoretical yield of 0.51 g ethanol per
g glucose. As per 68% glucan content (75.5% glucose) in SPW, the
Table 1
Glucose yield in microwave hydrothermal hydrolysis (%).
Microwave power Heating time for deionized water
1 min 2 min 3 min
550 W 2.6 4.1 5.6
700 W 4.8 7.7 8.8
900 W 7.0 11.1 9.1
a
ND – Not determined.
279
theoretical ethanol yield was expected to be 38.5 g ethanol per
100 g dry SPW.
3.2. Microwave hydrothermal hydrolysis
Microwave hydrothermal hydrolysis accelerated by carbon
dioxide was performed using different microwave power of 500,
700 and 900 W at heating times 1, 2, 3, and 5 min. The glucose
yield obtained from hydrothermal hydrolysis is reported in Table 1.
A maximum glucose yield of 43.8% which is 33.1 g per 100 g dry
SPW was attained with CO2 supplemented at 900 W and 2 min of
irradiation. However, the microwave hydrothermal hydrolysis
without CO2 produced a maximum glucose yield of 11.1% only,
which is 8.4 g per 100 g dry SPW at 900 W microwave power
and 2 min of irradiation. As in Table 1, using 700 W microwave
power, a maximum of 37.9% glucose yield was obtained at 3 min
heating with CO2. In addition, using 500 W microwave power a
maximum of only 32.7% glucose yield was only achieved at
5 min heating with CO2.
The comparison of maximum glucose yield obtained for differ-
ð2Þ
ent microwave power and heating time is shown in Fig. 1. This
shows the higher microwave power (900 W) and shorter irradia-
tion time (2 min) gives better glucose yield from SPW using hydro-
ð3Þ thermal hydrolysis with carbon dioxide. Furthermore, irradiation
time did have little effect on glucose yield as reported by Zhu
et al. [23] which is attributed to water evaporation. The reduction
ð4Þ in glucose yield was noticed at 700 W power with increasing heat-
ing time due to dehydration of glucose. The dehydration of glucose
resulted in formation of decomposition products in the hydrolysate
ð5Þ [16,18]. We observed that microwave irradiation supported by car-
bon dioxide enhanced the hydrothermal hydrolysis and increased
the glucose yield. A maximum of 32.7% increased glucose yield
was obtained compared to hydrothermal condition without carbon
dioxide. In addition, formation of byproducts such as acetic acid,
5-hydroxymethyl-2-furfural (5-HMF) and furfural concentration
decreased from 0.8%, 6% and 2.2% to 0.3%, 2% and 0.1%, respectively
using carbon dioxide. These were insufficient to produce any inhib-
ð6Þ itory effect during fermentation on S. cerevisiae [21]. Carbonic acid
generated from water and carbon dioxide acted as a catalyst to
break down the glucose molecules, it also controlled the formation
ð7Þ of byproducts, and assisted in lowering the pH level of hydrolysate
[18]. There was no evidence of xylose production. Solid fraction of
hydrolysate resulted in 9.8% and 9.5% xylan (hemicellulose) after
microwave hydrolysis without and with CO2, respectively.
However, only 3.1% lignin in hydrolysate after hydrolysis with
CO2 showed 40% of lignin was removed. Moreover, 18% untreated
glucan (starch and cellulose) also remained in the hydrolysate.
Miyazawa and Funazukuri [18] obtained 53% glucose yield from
raw starch at 200 °C for 15 min using hydrothermal hydrolysis
supported by CO2. But, we obtained 33.1 g glucose from 52 g bio-
mass starch which is 63.7% yield (g glucose/g biomass starch) in
the present study. As compared to previous studies reported in
sago pith waste [12,29–31], the glucose production was compara-
tively lower, however this method is energy efficient because of
combined pretreatment and hydrolysis in short time. The
Heating time for deionized water + CO2
5 min 1 min 2 min 3 min 5 min
6.1 14.7 18.5 28.6 32.7
8.5 19.3 25.9 37.9 36.7
ND 34.4 43.8 41.9 NDa
280 S.K. Thangavelu et al. / Applied Energy 128 (2014) 277–283
Fig. 1. Maximum glucose yield (%) for different (A) microwave power; (B) heating
time.
production cost of previous studies was high due to cost of enzyme
and ionic liquid, and high energy requirement (longer treatment
and hydrolysis time). In conclusion, the developed hydrolysis tech-
nique for SPW utilized less energy and cost in short time which sig-
nify a promising technique for the formation of glucose with
limited byproducts. Also this method is environmentally sustain-
able without the use of acid, base or enzyme catalyst which is suit-
able for different types of starchy biomass.
3.3. Ethanol fermentation and distillation
The batch fermentation was carried out with the different SPW
hydrolysates 7MH1, 7MH2, 9MH1, and 9MH2, and the comparison
of ethanol production is shown in Fig. 2. The highest ethanol con-
centration of 15.6 g/L was produced at 48 h fermentation from
9MH2 hydrolysate with 92.4% fermentation efficiency and 0.33 g/
L/h productivity. This result is comparable to the previous study
[30] that reported 93.29% fermentation efficiency obtained from
sago hampas hydrolysate produced by three cycle enzyme hydro-
lysis. However, 9MH1 hydrolysate produced an ethanol concentra-
tion of only 3.1 g/L at 60 h fermentation with 72% fermentation
efficiency and 0.05 g/L/h productivity. A maximum ethanol yield
(theoretical) of 40.5% which is 0.47 ethanol yield coefficient (g eth-
anol/g glucose) and 15.6 g per 100 g dry SPW, was obtained from
9MH2 hydrolysate. Moreover, 7MH2 and 7MH1 hydrolysates pro-
duced an ethanol concentration of 12.8 g/L and 2.4 g/L, respectively
(as in Table 2).
The comparison of fermentation kinetic parameters for different
hydrolysates is reported in Table 2. A decrease in ethanol yield was
observed after 60 h of fermentation perhaps due to oxidation or
evaporation of the ethanol. Furthermore, after distillation 15.2 g
pure fuel grade ethanol per 100 g biomass was obtained.
3.4. FTIR analysis
Fig. A1 (Appendix A. Supplementary) shows FTIR absorption
spectra of SPW before and after microwave hydrothermal hydroly-
sis supported by carbon dioxide. According to Lai et al. [32], the
peak 1735 cm1 (C@O stretching vibration) represents the complex
linkages between hemicellulose and lignin, such as ester-linked
acetyl, feruloyl, and p-coumaroyl groups. As observed from
Fig. A1(C), the IR spectra of SPW hydrolyzed (9MH2) becomes shar-
per and have reduced peak area meaning that the linkage were bro-
ken. The lignin triplicate peaks near 1427, 1453 and 1505 cm1
vanished. Lignin syringyl ring stretching near 1224 cm1 also
diminished. After microwave hydrothermal hydrolysis accelerated
by CO2 (9MH2), the polysaccharides peaks (765, 861, 925, 1054,
1158 and 1375 cm1) became sharper and some peaks disappeared
as compared with untreated SPW and 9MH1, corresponding to
appearance of monosaccharides such as glucose, fructose, and oli-
gosaccharides. FTIR transmission spectra of distilled ethanol (as in
supplementary Fig. A2) obtained from 9MH1 and 9MH2 showed
good evidence of OAH, CAH and CAO stretching presence at
3350, 2974 and 1045 cm1 respectively. It has good agreement with
the ethanol standards for OAH stretch of alcohols appearing in the
region 3500–3200 cm1 and the CAO stretch shown in the region
1260–1050 cm1.
3.5. GC analysis
The chromatography purification analysis of ethanol after distil-
lation showed only about 87% concentrated ethanol from the
hydrolysate produced without CO2 (9MH1), which showed about
13% water content and other substances. Whereas the ethanol con-
centration obtained from hydrolysate produced with CO2 (9MH2)
was about 96%. In addition, 3.7% methanol was also noticed in
the chromatography results.
3.6. Energy efficiency calculation
The energy consumption of microwave hydrothermal hydroly-
sis was calculated for 7MH1, 9MH1, 7MH2, and 9MH2 hydroly-
sates and reported in Table 3. The hydrolysate 9MH2 showed a
minimum energy consumption which was 33 kJ for producing 1 g
of glucose after microwave hydrothermal hydrolysis, and 69 kJ
for producing 1 g of ethanol after fermentation. In addition, 2.5 kJ
per 100 g biomass was used for grinding of SPW. In general, 1 g
ethanol can produce 30 kJ of energy and 1 g glucose can produce
16 kJ of energy.
In general, evaporation of 1 g of water requires 2.26 kJ and 1 g
of carbon dioxide requires 5.74 kJ at an initial temperature of
25 °C. We observed that the water loss in 9MH1 hydrolysate
was 12.4 g, and in 9MH2 hydrolysate was 7.2 g which mean
28.0 and 16.3 kJ was used for the water evaporation, respec-
tively. It was also observed that the CO2 loss in 9MH2 hydroly-
sate was 2.3 g which means 13.2 kJ was used for CO2
evaporation. Thus, up to 30% of the energy input was used for
 S.K. Thangavelu et al. / Applied Energy 128 (2014) 277–283 281

Fig. 2. Ethanol yield.

Table 2
Fermentation kinetic parameters for different microwave hydrolysates.

Experiment Glucose Ethanol Ferment. time Ethanol productivity Ferment. Ethanol yield coefficient (g/g Theoretical ethanol
no. (g/L) (g/L) (h) (g/L/h) efficiency (%) glucose) yield (%)
7MH1a 6.7 2.4 48 0.05 70 0.36 6.2
9MH1 8.4 3.1 60 0.05 72 0.37 8.1
7MH2 28.6 12.8 60 0.21 88 0.45 33.2
9MH2 33.1 15.6 48 0.33 92 0.47 40.5
a
7MH1 (700 W/3 min; H2O), 9MH1 (900 W/2 min; H2O) and 7MH2 (700 W/3 min; H2O + CO2), 9MH2 (900 W/2 min; H2O + CO2).

Table 3
Energy consumption for different microwave pretreatment and hydrolysis condition.

Experiment Microwave heating Energy consumption (kJ/g Energy consumption (kJ/g Water loss CO2 loss References
no. glucose) ethanol) (g) (g)
7MH1 Pretreatment and 188 525 16.3 – This study
hydrolysis
9MH1 Pretreatment and 128 348 12.4 – This study
hydrolysis
7MH2 Pretreatment and 44 98 14.8 1.8 This study
hydrolysis
9MH2 Pretreatment and 33 69 7.2 2.3 This study
hydrolysis
Ref. 1 Pretreatment only 5.5 10.9 10.3 – Lu et al. [24]
Ref. 2 Pretreatment only ND 29 NDa – Chen et al. [21]
a
ND – Not determined.

water and CO2 evaporation in 9MH2. It can be suggested that
higher biomass loading will have further controlled energy loss
due to water and CO2 evaporation, however ethanol yield might
be reduced [24]. In comparison with Awg-Adeni et al. [30], three
cycle enzymatic hydrolysis process utilized approximately 137 kJ
to produce 1 g glucose and 287 kJ to produce 1 g ethanol from
‘sago hampas’. In this study, the energy consumption for micro-
wave hydrothermal hydrolysis developed for SPW only utilized
33 kJ and 69 kJ to produce 1 g glucose and 1 g ethanol, respec-
tively. This is several times lower than previous studies
[21–24,30].
3.7. Overall mass balance
A complete mass balance diagram to describe the hydrothermal
hydrolysis of SPW into bioethanol by batch fermentation is shown
in Fig. 3. The optimal pretreatment and hydrolysis condition was at
900 W microwave power rating with a 2 min irradiation time
adding 120 g deionized water and 10 g dry ice to 10 g dry SPW
biomass. During hydrothermal hydrolysis 3.31 g glucose was
produced. The hydrolysate was recovered and batch fermentation
was performed with S. cerevisiae at 35 °C for 48 h. Fermentation
using S. cerevisiae successfully converted the glucose with 92%
282 S.K. Thangavelu et al. / Applied Energy 128 (2014) 277–283

fermentation efficiency, producing 1.56 g of ethanol per 10 g of

Fig. 3. Overall mass balance of sago pith waste (SPW).
SPW. These results validate that SPW can be a potential starchy
biomass material for fuel ethanol production using microwave-
enhanced hydrothermal hydrolysis and fermentation.
It is essential to compare the glucose and bioethanol production
from some starchy lignocellosic biomass reported previously. Ara-
poglou et al. [8] obtained only 1.85 g glucose and 0.76 g ethanol
from 10 g potato peel waste by enzymatic hydrolysis and fermen-
tation, even though it contains 52% starch and 16% cellulose. Su
et al. [7] obtained 3.41 g glucose and 1.4 g ethanol from 10 g sor-
ghum liquor waste and Rao et al. [9] produced 1.55 g ethanol from
10 g brewery waste water in which both contains enough starch in
chemical composition. In most of the previous studies [5–9]
enzyme hydrolysis at temperature ranges between 37 °C and
121 °C and hydrolysis time ranging from 1 h to 48 h were used.
Although the glucose and ethanol yield in the previous study
reported by Kosugi et al. [5] from cassava pulp and Oberoi et al.
[6] from banana peels were high, the energy used for the enzyme

Fig. A1. FTIR spectra of (A) untreated SPW, (B) 9MH1 and (C) 9MH2.

Fig. A2. FTIR spectra of distilled ethanol.

 S.K. Thangavelu et al. / Applied Energy 128 (2014) 277–283
hydrolysis was also high. In the present study the energy usage is
comparatively very low.
4. Conclusion
Using microwave hydrothermal hydrolysis accelerated by car-
bon dioxide a maximum of 44% glucose, which is 33.1 g per
100 g SPW, was obtained. A maximum of 41% theoretical ethanol
with 92% fermentation efficiency, which is 15.6 g ethanol per
100 g SPW, was obtained after fermentation. Furthermore, 15.2 g
ethanol per 100 g SPW with 96% concentration was obtained after
distillation. FTIR absorption spectra provided evidence of glucose
molecules breakdown during hydrolysis. The developed technique
for SPW is more energy efficient with limited byproducts
compared to previous techniques and suitable for commercial
fuel-grade ethanol production.
Acknowledgements
The authors are grateful to Universiti Teknologi Malaysia and
Universiti Malaysia Sarawak for their support and guidance.
Government of Sarawak Malaysia and Sarawak Biodiversity centre
Malaysia are also kindly acknowledged.
Appendix A. Supplementary material
See Figs. A1 and A2.
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