Applied Energy 122 (2014) 34–41

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

Enhancing methane production from rice straw by extrusion

pretreatment
Xiaohua Chen, YaLei Zhang ⇑, Yu Gu, Zhanguang Liu, Zheng Shen, Huaqiang Chu, Xuefei Zhou
State Key Lab of Pollution Control and Reuse, Tongji University, Shanghai 200092, China

h i g h l i g h t s

 Extrusion pretreatment had a significant effect on the particle size reduction.

 The physical priorities of rice straw were improved by extrusion pretreatment.
 The highest SMP obtained using the EPRS was 227.3 L/kg VS with an ISR of 0.4.
3 3 3
 The VMP obtained using the EPRS was 17.0 m /m with an SLR of 90 kg/m .
 SEM analyses indicated that the cellulose of the EPRS was devillicated.

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

Article history: Extrusion pretreatment was applied to enhance fermentative methane production from rice straw. The
Received 28 August 2013 extrusion-pretreated rice straw (EPRS) showed significant particle size reduction, physical properties
Received in revised form 13 November 2013 improvement and volume expansion, as compared to the milling-pretreatment rice straw (MPRS) and
Accepted 25 January 2014
unpretreated rice straw (UPRS). The anaerobic digestion of EPRS, MPRS and UPRS with different inocu-
Available online 27 February 2014
lum-to-substrate ratios (ISRs) and solid loading rates (SLRs) was investigated. The highest specific meth-
ane production (SMP) of the EPRS was 227.3 L/g VS with an ISR of 0.4 and SLR of 50 kg/m3, which was
Keywords:
32.5% and 72.2% greater than that of the MPRS and UPRS at the corresponding ISR and SLR, respectively.
Rice straw
Ligocellulosic biomass
Furthermore, the volumetric methane production (VMP) increased with increasing SLR. The highest VMP
Specific methane production (17.0 m3/m3) of the EPRS was obtained with an SLR of 90 kg/m3, which was 1.5 times that of the MPRS. In
Volumetric methane production addition, the EPRS had significantly shorter technical digestion time and higher cellulose and hemicellu-
Extrusion pretreatment lose degradation efficiencies, which was due to the smaller particle size and larger specific surface area of
the EPRS, thus contributing to the enhancement of methane production. The SEM analyses further dem-
onstrated that the cellulose of the rice straw was devillicated after extrusion pretreatment, which was in
agreement with the higher cellulose and hemicellulose degradation efficiencies of the EPRS.
Ó 2014 Elsevier Ltd. All rights reserved.

1. Introduction
In China, the 2011 energy consumption was 3.48 Gt standard
coals, of which coal, petroleum and natural gas was accounted for
68.4%, 18.6% and 5.0%, respectively [1]. The excessive consumption
of fossil fuels brings about a series of problems, such as the increas-
ing greenhouse gas concentration in the atmosphere, the worsening
of the global climate and the decreasing supply of fossil fuels. There-
fore, the exploration of new, sustainable and renewable energy to
replace exhaustible fossil fuels is urgent [2]. Lignocellulosic biomass
(agro-residues, forest-residues, etc.) is considered a primary candi-
date for producing bio-energy due to its abundant renewable
⇑ Corresponding author. Tel.: +86 21 65982503; fax: +86 21 65988885.
E-mail address: zhangyalei@tongji.edu.cn (Y. Zhang).
resources [3]. Crop straws (corn stover, wheat straw and rice straw)
are the major components of agro-residues in China [4]. The annual
output of crop straws in China is more than 0.7 billion tons and
about 0.5 billion tons (70.6%) are comprehensively utilized, among
which about 0.22 billion tons (31.9%) are used for animal feed,
0.11 billion tons (15.6%) for fertilizer plowing into field, 0.02 billion
tons (2.6%) for culture medium of edible fungi, 0.02 billion tons
(2.6%) for papermaking and artificial board, and 0.12 billion tons
(17.8%) for fuel (cooking, house heating, biogas and straw syngas)
[5]. Large amounts of unused crop straws are burnt in the open
fields, which both has a deleterious effect on the local air quality
and wastes biomass resources [4]. Rice straw is one of the most
abundant crop straws in central and southern China with an annual
yield of nearly 0.3 billion tons [6]. As a typical lignocellulosic bio-
mass, rice straw is mainly composed of cellulose (appr. 34 wt%)

http://dx.doi.org/10.1016/j.apenergy.2014.01.076
0306-2619/Ó 2014 Elsevier Ltd. All rights reserved.
 X. Chen et al. / Applied Energy 122 (2014) 34–41
Nomenclature
AD anaerobic digestion
C/N carbon to nitrogen ratio
Cb,i the methane content of the blank control, %
Ce,i the methane content of the experimental
group, %
Cellulosede the degradation efficiency of cellulose, %
Cellulosers the cellulose content of the rice straw, %
CH4 methane
CMP cumulative methane production
CO2 carbon dioxide
EPRS extrusion pretreated rice straw
Hemicellulosede the degradation efficiency of hemicellulose, %
Hemicellulosers the hemicellulose content of the rice straw, %
ISR inoculum to substrate ratio, VS/VS
MMP maximal methane production
MPRS milling pretreated rice straw
SEM scanning electron microscopy
SLR solid loading rate, kg/m3
SMP specific methane production, L/kg VS
T80 technical digestion time, d
TC total carbon
TN total nitrogen
making up by the same anhydroglucose units, hemicellulose (appr.
28 wt%) consisting of different polymers like pentoses and hexoses,
and lignin (appr. 10 wt%) forming a three-dimensional network by
phenylpropane units [7,8]. It is an organic-rich material and can
be used as potential feedstock for bioenergy [7,9].
Recently, the biological production of methane, hydrogen, etha-
nol and other biofuels from straw has drawn much attention [9–
13]. Methane is the main component of biogas, which is produced
using anaerobic digestion (AD) by a variety of microorganisms to
decompose organic matter under oxygen-free conditions [14]. AD
usually involves four stages (hydrolysis, acidogenesis, acetogenesis
and methanogenesis) [15]. Among the four stages, hydrolysis is
usually considered the rate-limiting step, which affecting the con-
version efficiency of straw. Many studies focused on accelerating
straw hydrolysis and increasing the methane yield by physical,
chemical, biological or physicochemical pretreatment methods
[16–20]. Each pretreatment method has advantages and disadvan-
tages, and there is no ‘‘ideal’’ method [8]. Physical pretreatment
can reduce the particle size and increase the surface area and
pore-size by releasing intercellular components which increases
the hemicellulose hydrolysis and further accelerates cellulose
hydrolysis, but it is higher energy-demanding [8]. Hence, physical
pretreatment like milling is less attractive in practical application.
Chemical pretreatment with acid, alkali or aqueous ammonia is
simple, quick, and effective at changing the chemical compositions
of the biomass and increasing surface accessibility for anaerobic
microorganisms by decreasing cellulose crystallinity [21–23], but
it increases the cost and causes secondary pollution [24]. Even
worse, inhibitors or toxic substances such as furfural, hydroxym-
ethylfurfural, levulinic and phenolic compounds are always
produced in the chemical pretreatment [8,25]. Biological pretreat-
ment using microorganisms (white, brown and soft rot-fungi) is
energy-saving and uses mild operation conditions, but it requires
a long residence time to degrade the lignin; additionally, it is diffi-
cult for large-scale applications [8,18,24].
However, as particle sizes larger than 2 mm limit the heat and
mass transfer during hydrolysis [26], particle size reduction is nec-
essary for straw to produce methane. In addition, particle size
reduction can increase the specific surface area and bulk density
and decrease the volume of straw. The biomass size reduction
35
TS total solid
TSb the TS content of the digested residues of the
blank control, %
TSde the degradation efficiency of TS, %
TSrs the TS content of the rice straw, %
UPRS unpretreated rice straw
V/V volume to volume
Vb,i the biogas volume of the blank control, ml
Ve,i the biogas volume of the experimental group, ml
Vw working volume, ml
VMP volumetric methane production, m3/m3
VS volatile solid
VSb the VS content of the digested residues of the
blank control, %
VSde the degradation efficiency of VS, %
VSrs the VS content of the rice straw, %
Wb the weight of the digested residues of the blank
control, g
Wre the weight of the digested residues of the exper-
imental group, g
WHC water-holding capacity, g/g
equipment include a shredder, ball mill, hammer mill, knife mill,
disc mill, two roll mill, colloid mill and extruder [26]. In addition
to size reduction, the extruder can provide a continuous thermo-
mechanical treatment, which is widely employed as a mechanical
pretreatment method for lignocellulosic biomass ethanol produc-
tion, pulping and papermaking [27,28]. Recently, the extruder, as
a novel and promising machine, has been used for biomass conver-
sion to methane [29,30]. During the extrusion pretreatment pro-
cess, the biomass is subjected to shearing, heating and mixing,
disrupting the lignocellulose structure and resulting in the defibril-
lation, fibrillation and shortening of the fibers [26]. The physical
and chemical change after extrusion pretreatment makes the
cellulose and hemicellulose accessible to enzymatic attack and in-
creases the methane production [26]. Hjorth et al. (2011) investi-
gated the extrusion pretreatment of five agricultural biomass
types prior to producing methane and found that the methane pro-
duction increased by 9–28% after 90 days and resulted in energy
surpluses of 6–68% after subtracting the energy consumed by the
extruder [29]. Other pretreatments like milling, thermal, acid, alka-
line, hydrothermal and white-rot fungi pretreatment have been
intensively reported [10,16,18,19,22]. However, there is little infor-
mation about the effect of the extrusion pretreatment of rice straw
on methane production.
Therefore, the major objective of this study was to investigate
the influence of extrusion pretreatment on methane production
from rice straw, a typical lignocellulosic biomass. Furthermore,
the physical properties, such as particle size distribution, bulk den-
sity, water-holding capacity, specific porosity and specific surface
area, were determined after extrusion pretreatment, and the
chemical composition was also analyzed. In addition, the mecha-
nism of the extrusion pretreatment for significantly elevated meth-
ane production from rice straw was explored.
2. Methods
2.1. Feedstock and inoculum
The rice straw used in this study was collected from Yancheng
city, Jiangsu province, China, and dried at room temperature. The
dried rice straw was then cut into 50-mm sections by a paper
36 X. Chen et al. / Applied Energy 122 (2014) 34–41
trimmer as the unpretreated rice straw (UPRS) and stored in an air-
tight plastic bag before pretreatment and anaerobic digestion
experiments. The characteristics of the rice straw were summa-
rized in Table 1. The inoculum was anaerobic sludge taken from
an anaerobic digester treating dairy manure in Shanghai city and
stored at 4 °C in the refrigerator before use. It contained 15.1% total
solids (TS) and 11.5% volatile solids (VS).
2.2. Extrusion pretreatment
Extrusion pretreatment was performed using a twin-screw
extruder (JXM80, Jinwor Machinery Co., Ltd., Nanjing, China). The
extruder, with a rotating speed of 120 rpm, was driven by a
55-kW monitor and was a combination of a subsequent transport
screw, reversed screw element and transport screw. The length
and diameter of the transport screws were 30.0 and 8.0 cm, respec-
tively, having a length/diameter ratio of 3.75. The rice straw was
continuously fed into the barrel through the inlet orifice by trans-
port screws, accumulated and compressed in the space between
the transport screws and the reversed screw element. A total of
2.0 kg of UPRS was fed into the extruder, and all of the extrusion
pretreatment rice straw (EPRS) was collected. For comparison with
extrusion pretreatment, a laboratory-scale hammer mill was used
to treat approximately 2.0 kg of UPRS. All the pretreated rice straw
was collected and stored in an airtight plastic bag at room temper-
ature for later analysis of the physical properties and chemical
compositions and anaerobic digestion experiments.
2.3. Methane production
The UPRS, milling-pretreatment rice straw (MPRS) and EPRS
were digested in batch for methane production. All the batch
experiments were conducted in series of wild-mouth bottles func-
tioning as anaerobic digesters. The total volume of the anaerobic
digester was 500 ml, with a working volume (Vw) of 400 ml.
2.3.1. Methane production at different ISRs
Four different inoculum-to-substrate ratios (ISRs; 0.2, 0.3, 0.4
and 0.5) based on the VS for the UPRS, EPRS and MPRS were studied.
First, 20.0 g of TS (UPRS, EPRS and MPRS) was weighed and mixed
thoroughly with the required amount of inoculum and then fed into
the digester. Second, a certain amount of urea was dissolved in
distilled water and then added to the mixture to adjust the car-
bon-to-nitrogen ratio (C/N) to 25, which is optimal for anaerobic
microorganisms growth [16]. Third, each digester was flushed with
nitrogen for 60 s to remove oxygen and immediately sealed tightly
with rubber stoppers. Finally, all the digesters were then placed in a
walk-in incubator at a constant mesophilic temperature (37 ± 1 °C)
for 60–90 days. A blank control containing only inoculum and dis-
tilled water was used to correct for the methane from the inoculum.
All experiments were conducted in triplicate, and the results
reported were the average of triplicate tests.
Table 1
Characteristics of rice straw used in this study.
Parameter Valuesa
Total solid (TS%) 90.3 ± 0.2
Volatile solid (VS, TS%) 85.7 ± 0.4
Total carbon (TC, TS%) 41.7 ± 0.1
Total nitrogen (TN, TS%) 0.6 ± 0.0
Carbon to nitrogen ratio (C/N) 69.5 ± 0.2
Cellulose (TS%) 30.0 ± 1.1
Hemicellulose (TS%) 29.8 ± 0.9
Lignin (TS%) 6.5 ± 0.4
a
Data are the means of triplicate measurements ± standard
deviations.
2.3.2. Methane production at different SLRs
The SLR was defined as the amount of the rice straw dry matter
fed per unit digester Vw [17]. As the bulk density of the UPRS was
lower than that of the EPRS and MPRS (see Table 3), three SLRs (10,
30 and 50 kg/m3) were applied for the UPRS and five SLRs (10, 30,
50, 70 and 90 kg/m3) for the MPRS and EPRS. According to the SLR,
required amount of the UPRS, EPRS and MPRS were mixed thor-
oughly with the appropriate amount of inoculum to obtain an
ISR of 0.4 based on the VS. After the mixture was fed into each di-
gester, all other operations were the same as described in 2.3.1.
2.4. Analytical methods
2.4.1. Physical properties
Five standard sieves (aperture sizes of 5.0, 2.5, 0.85, 0.45 and
0.28 mm) and a bottom plate were used to measure the particle
size distributions of the UPRS, EPRS and MPRS. The bulk density,
specific porosity and water-holding capacity (WHC) were deter-
mined as reported previously [31]. The specific surface area was
detected with a Brunauer–Emmett–Teller surface area analyzer
(3H-2000BET-A, Beishide Instrument S&T Co., Ltd., Beijing, China)
using nitrogen adsorption at 77 K.
2.4.2. Scanning electron microscopy (SEM) analysis
The cellulose of the UPRS and EPRS was separated according the
method given by Krschner and Hoffer [32]. The morphology of the
cellulose was observed with a scanning electron microscope (SEM;
Quanta 200 FEG, Japan).
2.4.3. Chemical composition
TS, VS and ash were in accordance with the Standard Methods
for the Examination of Water and Wastewater [33]. The total
carbon (TC) and total nitrogen (TN) were determined using an ele-
mental analyzer (Vario EL III, Elementar, Germany). The cellulose,
hemicellulose and lignin were determined according to the meth-
od of Van Soest [34].
2.4.4. Methane production
The biogas production volume was monitored by the water dis-
placement method. The gas component was measured using a gas
chromatograph (GC-14B, Shimadzu, Japan) equipped with a ther-
mal conductivity detector with nitrogen as the carrier gas. The flow
rate of nitrogen was 15 ml/min. The temperatures of the injection
port and detector were 150 and 190 °C, respectively. A standard
gas consisting of 60% (V/V) CH4 and 40% CO2 was used for gas chro-
matography calibration.
2.5. Calculation methods
The methane production was adjusted to the volume at stan-
dard temperature and pressure (273 K, 101.325 Pa). The specific
methane production (SMP) was presented as the volume of meth-
ane produced based on the initial total VS of the feedstock. The vol-
umetric methane production (VMP) was defined as the maximal
methane production (MMP) per unit digester Vw. The SMP and
VMP were calculated using the following equations:
Pi¼t
 C e;i  V b;i  C e;i Þ
i¼1 ðV e;i
SMP ¼ ð1Þ
SLR  V w  TSrs  VSrs
VMP ¼ MMP=V w ð2Þ
where Ve,i and Vb,i are the biogas volume of the experimental group
and the blank control, respectively, at the measured time, ml; Ce,i
and Cb,i are the methane content of the experimental group and
 X. Chen et al. / Applied Energy 122 (2014) 34–41
the blank control, respectively, %; Vw is the working volume of the
digester, ml; and t is the digestion period, d.
The degradation efficiency of TS, VS, cellulose and hemicellulose
were calculated using the following equations:
ðSLR  Vw  TSrs  Wre  TSre  Wb  TSb Þ
TSde ¼
SLR  Vw  TSrs
ðSLR  Vw  TSrs  VSrs  Wre  TSre  VSre  Wb  TSb  VSb Þ
VSde ¼ ð4Þ
SLR  Vw  TSrs  VSrs
ðSLR  Vw  TSrs  Cellulosers  Wre  TSre  Cellulosere Þ
Cellulosede ¼
SLR  Vw  TSrs  Cellulosers
ð5Þ
ðSLR Vw  TSrs Hemicellulosers Wre TSre Hemicellulosere Þ
Hemicellulosede ¼
SLR Vw TSrs Hemicellulosers
ð6Þ
where TSde, VSde, Cellulosede and Hemicellulosede are the degrada-
tion efficiency of TS, VS, cellulose and hemicellulose, respectively,
%; TSrs, VSrs, Cellulosers and Hemicellulosers are the TS, VS, cellulose
and hemicellulose contents of the rice straw, respectively, %; Wre
and Wb are the weights of the digested residues of the experimental
group and blank control, respectively, g; TSb and VSb are the TS and
VS contents, respectively, of the digested residues of the blank con-
trol, %; and TSrs, VSrs, TSre, VSre, Cellulosere and Hemicellulosere are,
respectively, the TS, VS, cellulose and hemicellulose contents of the
digested residues of the experimental group, %.
2.6. Statistical analysis
All the anaerobic digestion experiments were conducted in trip-
licate, and the results were the means of the three measurements.
SAS 8.1 software (SAS Institute Inc., Cary, NC, USA) was employed
to analyze the standard deviations and significant differences.
3. Results and discussion
3.1. Extrusion pretreatment
3.1.1. Particle size distributions
Preliminary experiments were performed to study the effects of
the rice straw length (50, 100, 150 and 200 mm) and moisture con-
tent (10%, 40%, 60% and 80%) on the size reductions of the extru-
sion pretreatment. Both the rice straw length and moisture
content had significant effects. The smaller the rice straw and the
lower the moisture content fed into the extruder, the larger the
size reduction of the rice straw obtained. Hence, the rice straw
was cut into 50-mm pieces as the UPRS, and no water was used
to adjust the moisture content for the extrusion pretreatment.
The UPRS, MPRS and EPRS were presented in Fig. 1a–c, respec-
tively. Obviously, the UPRS had relatively large particle size. After
milling and extrusion pretreatment, the particle size of the MPRS
and EPRS had significant reduction. The particle size distributions
of the UPRS, MPRS and EPRS were summarized in Table 2. Approx-
imately 90.5% and 77.4% of the EPRS particles were below 2.5 and
0.85 mm in size, respectively, which were 20.6% and 25.4% higher
than the corresponding values for the MPRS particles. This finding
showed that the extrusion pretreatment had a significant effect on
the particle size reduction. Similar results were reported by a pre-
vious study, which found that particles larger than 1 mm were
present at 5–50% after extrusion pretreatment [29].
37
3.1.2. Physical properties
The bulk density of the UPRS was within the literature range of
55–65 kg/m3 [35]. After pretreatment, the bulk density of the rice
straw increased significantly for the EPRS and MPRS (see Table 3),
which were 2.15 and 2.40 times greater than that of the UPRS,
respectively. The higher bulk density of the EPRS and MPRS was
ð3Þ
in agreement with the smaller particle size (see Table 2). As the
bulk density is defined as the weight (based on dry mass) of mate-
rial per unit volume, general speaking, the smaller particle size of
the rice straw leads to the smaller volume and the higher bulk den-
sity [31]. However, the EPRS had a smaller particle size but a lower
bulk density than the MPRS, which may reflect the expansion of
the rice straw during the extrusion pretreatment.
The specific porosity is an indicator of structural modification of
the rice straw. General speaking, an increased specific porosity
suggests the expansion of the rice straw, whereas a decreased spe-
cific porosity suggests the contraction of rice straw [31]. As shown
in Table 3, the specific porosity of the EPRS was higher than that of
the MPRS, which also indicated that the rice straw expanded after
the extrusion pretreatment. The smaller particle size and the
expansion of the EPRS resulted in a larger specific surface area
(see Table 3) than that of the MPRS and UPRS.
Cellulose accessibility is an important characteristic of lignocel-
lulosic biomass and can be represented using the water-holding
capacity (WHC). The WHC of the EPRS was higher than that of
the MPRS, implying that more surfaces were exposed after extru-
sion pretreatment [36]. This finding was also in conformity with
the increase in the specific surface area of the EPRS.
3.1.3. SEM analysis
Although extrusion pretreatment had a significant effect on the
particle size reduction, large particles still remained after the
extrusion pretreatment (Fig. 1d). However, their appearances were
significantly different from those of the UPRS (Fig. 1a). The average
width of the EPRS was below 0.2 mm, while the average width of
the UPRS was 4.8 ± 0.9 mm. This difference indicated that the
extrusion pretreatment not only cut but also tore the rice straw,
resulting in shorter and narrower rice straw pieces after extrusion
pretreatment. To investigate the structural change caused by the
extrusion pretreatment, the cellulose extracted from the UPRS
and EPRS was subjected to SEM analysis. Compared with the cellu-
lose of the UPRS (Fig. 1e), it was observed that defibration appeared
in the EPRS (Fig. 1f). In general, a typical extruder is comprised of
feed, compression and expansion/wearing zones. During the extru-
sion pretreatment, the extruder can provide dynamic compression,
effective biomass mixing, rapid heat transfer and vigorous shear
forces upon pressure release, which caused the defibration, fibrilla-
tion and size reduction of lignocellulosic biomass [26,29].
3.2. Methane production
3.2.1. SMP
The ISR is an important factor that directly affects the methane
production. If the inoculum content is below the required amount,
methane production drops or even stops. Fig. 2a demonstrates the
effects of the four different ISRs (0.2, 0.3, 0.4 and 0.5) on the SMP of
the UPRS, MPRS and EPRS. For all the rice straw samples, an ISR of
0.2 gave a much lower SMP than the other three ISRs tested. The
low ISR may be a result of the digester’s failure to produce methane
with only 67.1, 88.9 and 109.7 L/kg VS of SMP, respectively, for the
UPRS, MPRS and EPRS. Increasing the ISR from 0.2 to 0.5 resulted in
a significant improvement in the SMP. The maximal SMP was pro-
duced by the EPRS at an ISR of 0.4, which was 110.0% greater than
that at an ISR of 0.2. At an SLR of 0.4, the SMP was 227.3 L/kg VS for
the EPRS, which was 72.2% and 32.5% greater than that of the UPRS
and MPRS at the corresponding ISRs. When the ISR was increased
38 X. Chen et al. / Applied Energy 122 (2014) 34–41

a b c d

e f

Fig. 1. The images of (a) UPRS, (b) MPRS, (c) and (d) EPRS, SEM micrographs of cellulose extracted from (e) UPRS and (f) EPRS.

Table 2
Particle size distributions of the UPRS, MPRS and EPRS.

Particle size distributions (wt.%)a

5–50 mm 2.5–5 mm 0.85–2.5 mm 0.45–0.85 mm 0.28–0.45 mm <0.28 mm
UPRS 100.0 ± 0.0 – – – – –
MPRS 22.0 ± 0.1 18.1 ± 0.3 17.7 ± 0.2 21.5 ± 0.7 13.9 ± 0.1 6.8 ± 0.6
EPRS 3.0 ± 0.3 6.5 ± 0.5 13.1 ± 0.8 22.3 ± 0.1 22.1 ± 0.6 33.1 ± 1.1
a
Data are the means of triplicate measurements ± standard deviations.

Table 3
Physical properties of the UPRS, MPRS and EPRS.a

Parameter Unit UPRS MPRS EPRS

Bulk density (based on TS) kg/m3 61.2 ± 3.2 146.7 ± 2.2 131.4 ± 3.8
Water-holding capacity (WHC)b g/g 1.87 ± 0.0 1.87 ± 0.0 2.29 ± 0.0
Specific porosityb ml/g 8.08 ± 0.3 8.08 ± 0.3 9.12 ± 0.4
Specific surface area m2/g 0.77 ± 0.2 1.02 ± 0.1 1.15 ± 0.1
a
Data are the means of triplicate measurements ± standard deviations.
b
The UPRS, MPRS and EPRS were milled and screened with 40-mesh screen, and only the particles remained on the screen were used for analysis.

to 0.5, there was no significant difference in the SMP for the UPRS,
MPRS and EPRS compared to the ISR of 0.4. Hashimoto et al. (1989)
observed that an ISR of less than 0.25 drastically reduced the meth-
ane yield when using ball-milled wheat straw to evaluate the effect
of ISR on methane production in batch experiments [37].
The SMPs of the UPRS, MPRS and EPRS at different SLRs were
also investigated, and the results were shown in Fig. 2b. There
was a significant difference (p < 0.05) in the SMP between the EPRS,
MPRS and UPRS at different SLRs. The SMPs of the EPRS were 72.2–
99.5% greater than those of the UPRS at an SLR of 10–50 kg/m3 and
44.8–61.0% more than those of the MPRS at an SLR of 10–90 kg/m3.
The results demonstrated that the SMP of rice straw was signifi-
cantly greater after extrusion pretreatment [29].
the VMP was utilized in this study. Fig. 3 presented the VMP of the
UPRS, MPRS and EPRS at different SLRs. At SLRs of 10–50 kg/m3, the
VMP of the EPRS was 1.7–2.0 times that of the UPRS, which also
proved that the extrusion pretreatment enhanced the methane
production. As the UPRS contains large particles and has a low bulk
density (see Tables 2 and 3), SLRs above 50 kg/m3 were unsuitable
for the UPRS but were appropriate for the MPRS and EPRS. The
maximal VMPs of the MPRS and EPRS at an SLR of 90 kg/m3 were
17.0 and 11.3 m3/m3, respectively. This finding also indicated that
extrusion pretreatment was more effective than milling pretreat-
ment. The higher VMP meant that the digester produced more en-
ergy during the digestion period, which is meaningful in the
application of extrusion pretreatment [26].

3.2.2. VMP 3.2.3. Technical digestion time (T80)

The SMP is usually used to evaluate the utilization efficiency of The technical digestion time (T80) is the time needed to produce
the feedstock, while volumetric methane production (VMP) is a 80% of the MMP [38]. It is a critical indicator of the rice straw
good indicator of the digester efficiency. As the methane content anaerobic digestion used to evaluate the different pretreatment ef-
is variable and most of the energy contained in biogas is methane, fects. Hence, the T80 was also investigated in this study and was
 X. Chen et al. / Applied Energy 122 (2014) 34–41 39

a UPRS MPRS EPRS UPRS

250
100%
MPRS
SMP (L/kg VS)

200
80% EPRS

CMP / MMP
150 60%

100 40%

50 20%

0 0%
0.2 0.3 0.4 0.5 0 10 20 30 40 50 60 70 80 90

Inoculum to substrate ratio (VS/VS) Time (d)

Fig. 4. T80 of the UPRS, MPRS and EPRS with an SLR of 50 kg/m3. CMP: cumulative
methane production; MMP: maximal methane production. Error bars represent
b UPRS MPRS EPRS standard deviations of triplicate tests.
250

straw. After pretreatment, the chemical compositions of the EPRS

SMP (L/kg VS)

200
and MPRS had not changed [29]. However, the cellulose and hemi-
150 cellulose were degraded during the anaerobic digestion period. The
TS, VS, cellulose and hemicellulose degradation efficiencies were
100 shown in Fig. 5. The highest TS, VS, cellulose and hemicellulose
degradation efficiencies were obtained for the EPRS, being 6.6%,
50 14.7%, 20.0% and 8.9% higher than those of the MPRS and 22.0%,
25.7%, 26.6% and 27.0% higher than those of the UPRS, respectively.
0 The degradation efficiencies of the EPRS, MPRS and UPRS were sig-
10 30 50 70 90 nificantly different. The higher TS, VS, cellulose and hemicellulose
Solid loading rate (kg/m3) degradation efficiencies of the EPRS were correlated with the high-
er SMP and also indicated that the effect of the extrusion pretreat-
Fig. 2. Effects of the (a) ISR and (b) SLR on the SMPs of the UPRS, MPRS and EPRS. ment was more than just the size reduction of the rice straw. In
Error bars represent standard deviations of triplicate tests. addition, the EPRS exhibited very high cellulose degradation,
which was in agreement with Fig. 1f and Table 3, which indicated
that the cellulose was devillicated and had a higher specific surface
UPRS MPRS EPRS area after extrusion pretreatment.

15
3.3. Mechanism of extrusion pretreatment
VMP (m³/m³)

10 Extrusion pretreatment was used to enhance the methane pro-

duction from rice straw. The results of this study and others were
compared in Table 4. The highest SMP of the EPRS was obtained at
5
an SLR of 50 kg/m3 and was in the range of 59.8–290.0 L/kg VS
[10,16,18,19,39]. It is well known that anaerobic digestion is a
complex biochemical process, and many factors have an effect on
0
10 30 50 70 90 the SMP, including the pretreatment methods, particle size, SLR,
Solid loading rate (kg/m 3) ISR, and origin of the rice straw [8]. The SMP of the EPRS reported
in this study was relatively high compared to the literature values,
Fig. 3. VMP of the UPRS, MPRS and EPRS with different SLRs. Error bars represent
standard deviations of triplicate tests.

presented in Fig. 4 for each treatment. It was observed that T80 was TS VS Cellulose Hemicellulose
Degradation efficiency

67, 50 and 32 days for the UPRS, MPRS and EPRS, respectively. The 80%
T80 was significantly reduced for the EPRS compared to the UPRS
and MPRS. This finding demonstrated that the EPRS was more 60%
accessible and readily biodegradable for the anaerobic microorgan-
isms, thus accelerating hydrolysis of the EPRS and shortening the 40%
digestion period. The T80 for the EPRS was comparable to the find-
ing of a previous study, which reported that the T80 for 2%, 4% and
20%
6% NaOH pretreated corn stover at an SLR of 50 kg/m3 was 32, 28
and 38 days, respectively [17].
0%
UPRS MPRS EPRS
3.2.4. Degradation of TS, VS, cellulose and hemicellulose
The chemical compositions of rice straw were presented in Fig. 5. TSde, VSde, Cellulosede and Hemicellulosede of the UPRS, MPRS and EPRS with
Table 1. Cellulose and hemicellulose accounted for 59.8% of the rice an SLR of 50 kg/m3. Error bars represent standard deviations of triplicate tests.
40 X. Chen et al. / Applied Energy 122 (2014) 34–41

Table 4
Comparison between the results of this study and others.

Feedstock Particle size (mm) Pretreatment SLR (kg/m3) ISR (VS/VS) SRT (d) Temperature (°C) SMP VMP (m3/m3) Reference
(L/kg VS)
Rice straw <50 Extrusion 50.0 0.4 60 37 ± 1 227.3 9.7 This study
Rice straw <50 Extrusion 90.0 0.4 60 37 ± 1 218.1 17.0 This study
Rice straw <1 – 50.0 1.0 40 37 59.8 2.4b [19]
Rice straw <1 3% NaOH 50.0 1.0 40 37 74.1 3.2b [19]
Rice straw <1 Hydrothermal and 5% NaOH 50.0 1.0 40 37 132.7 6.4b [19]
Rice straw 3–5 – 14.6 0.3a 120 22 ± 1 270.0–290.0 3.6b [10]
Rice straw 70–80 White-rot fungi 49.4a – 89 Ambient 239.7 9.79b [18]c
Rice straw 200–600 – 46.5a – 189 30–40 231.0 9.45b [37]c
Rice straw 10–25 Grounded/thermal 50 – 24 35 ± 1 190.0– 3.8–4.9b [16]d
244.9a
Rice straw 25 Chopped 75 – 24 35 ± 1 187.8a 5.6b [16]d
Rice straw 25 Chopped 100 – 24 35 ± 1 212.1a 8.4b [16]d
a
Values calculated from the reference.
b
Values calculated from the reference by Eq. (2).
c
One-phase, solid leaching bed digester.
d
Two-phase, anaerobic sequencing batch digester. The working volumes of the first and the second phase all were 4.0 L.

which indicated that extrusion pretreatment was an effective pre-
treatment method. In addition, the highest VMP (17.0 m3/m3) of
the EPRS was obtained at an SLR of 90 kg/m3, which is significantly
higher than other reported data. Therefore, it is necessary to
explore the mechanism of the extrusion pretreatment.
First, the extrusion pretreatment led to a significant size reduc-
tion in the rice straw and increased the WHC, thus improving the
accessibility and providing a greater surface area for the anaerobic
microorganisms in the digestion period, leading to higher anaerobic
digestibility of the rice straw [36]. The smaller particle size (see
Table 2) and larger surface area (see Table 3) of the EPRS facilitate
enzymatic attack and accelerate the hydrolysis rate [26,29], thus
enhancing the SMP of the rice straw. Møller et al. (2004) found that
the methane productivity of straw cut to a maximum length of
1 mm (161 ± 10 L/kg VS) was significantly higher than that of straw
cut to a maximum length of 30 mm (145 ± 3 L/kg VS) [40]. Zhang
et al. (1999) found that the biogas yield achieved by grinding the
straw into 10-mm pieces was 17.5% higher than that of the whole
straw [16]. The milling pretreatment also affected the size reduction
(see Table 2). However, the SMP of the MPRS was significantly lower
than that of the EPRS, indicating that the effect of the extrusion pre-
treatment was more than just a size reduction of the rice straw.
Second, the physical properties of the EPRS changed. Extrusion
pretreatment is a physical pretreatment method, which is different
from chemical and biological pretreatment. During the chemical
pretreatment, the chemical compositions and structures of the
biomass are usually changed. He et al. (2008) reported that the
cellulose, hemicellulose and lignin of the rice straw were degraded
of 16.4%, 36.8% and 28.4%, respectively, after solid state sodium
hydroxide pretreatment [7]. Moreover, after hydrolysis the ester
bond of lignin-carbohydrate complexes was significantly de-
stroyed [7]. Biological pretreatment using white-rot fungi could
degrade lignin and destroy the lignocellulose structure [18]. The
removal/degradation of lignin made the lignocellulosic biomass
more available and biodegradable for the anaerobic microorgan-
isms, thus enhancement of methane production [8]. Unlike
chemical and biological pretreatment, however, the chemical com-
positions of the EPRS were the same as those of the UPRS and
MPRS. Nonetheless, the physical properties of the EPRS, such as
the bulk density, WHC, specific porosity and specific surface area,
were extremely different from those of the UPRS and MPRS. The in-
crease in the surface area, specific porosity and WHC made the
EPRS more available for enzymatic attack and thus accelerated
the hemicellulose and cellulose hydrolysis (see Fig. 4), resulting
in an increase in the SMP. In addition, the higher bulk density of
the EPRS compared with the UPRS allowed more rice straw to be
fed to the digester, providing more VS to produce methane [40],
thus significantly enhancing the VMP. Moreover, it should be noted
that the EPRS exhibited volume expansion, as indicated by the de-
crease in the bulk density and increase in the specific porosity and
specific surface area (see Table 3), which also indicated the physi-
cal properties change of the EPRS.
Finally, the cellulose of the EPRS showed obvious devillication
(see Fig. 1f), leading to more cellulose exposed to anaerobic micro-
organisms during the digestion period, thus contributing to the
higher SMP of the EPRS. It is well known that the biodegradability
of the ligocellulosic biomass is restricted by several factors like
particle size, available surface area and lignin content [8]. Above
all, lignin is the most resistant part of the ligocellulosic biomass
to anaerobic microorganisms and is the biggest barrier to degrade
cellulose, for the cellulose is embedded in a matrix of lignin and
hemicellulose [2]. Although the extrusion pretreatment could not
remove or degrade lignin like chemical and biological pretreat-
ment, the cellulose of the EPRS was shorten and devillicated (see
Table 2 and Fig. 1f) by dynamic compression and vigorous shear
forces upon pressure release during the extrusion pretreatment.
The cellulose fiber devillication is the unique phenomenon found
in the extrusion pretreatment, which is evident different from
other physical pretreatment (milling, thermal and hydrothermal),
chemical pretreatment (acid, alkali and aqueous ammonia), and
biological pretreatment (white, brown and soft rot-fungi). In
Table 1, it can be observed that the cellulose, hemicellulose and lig-
nin accounted for 65.3% of the rice straw TS. As the lignin and ash
was nondegradable for the anaerobic microorganisms, the greater
cellulose degradation resulted in higher TS, VS and cellulose degra-
dation efficiencies and increased the SMP of the EPRS.
In conclusion, the mechanism of extrusion pretreatment was
not due to change the chemical compositions and structures of
the rice straw, but significantly change the physical properties
(particle size distributions, WHC, specific porosity and specific sur-
face area, etc.) and obvious devillication of the cellulose fiber,
which accelerated the hemicellulose and cellulose hydrolysis and
led to higher cellulose and hemicellulose degradation efficiencies,
thus contributing to the enhancement of methane production from
rice straw.
4. Conclusions
The effects of extrusion pretreatment on methane production
from rice straw with different ISRs and SLRs were investigated.
The highest SMP of the EPRS was 227.3 L/kg VS at an SLR of
50 kg/m3, and the highest VMP (17.0 m3/m3) was obtained at an
 X. Chen et al. / Applied Energy 122 (2014) 34–41
SLR of 90 kg/m3. After extrusion pretreatment, the chemical
compositions of the rice straw had not changed, while the particle
size and the physical properties, such as the bulk density, WHC,
specific porosity and specific surface area, were different from
those of the UPRS and MPRS. Meanwhile, the cellulose extracted
from the EPRS was subjected to SEM analysis, which further
indicated that the cellulose was devillicated after the extrusion
pretreatment, resulting in an improvement in the SMP. This finding
was confirmed by the high cellulose degradation efficiency of the
EPRS. Thus, extrusion pretreatment could be potentially used for
enhancing methane production from lignocellulosic biomass.
Acknowledgments
The authors are grateful to the Ministry of Science and Technol-
ogy of the People’s Republic of China for supporting this research.
This study was financially supported by the National Natural
Science Foundation of China (Nos. 20976139, 21246001,
51138009), the National Key Technologies R&D Program of China
(No. 2012BAJ25B02), New Century Excellent Talents in University
(NCET-11-0391) and the Project of Shanghai Science and Technol-
ogy Commission (No. 11QH1402600). We also very much appreci-
ate the critical and constructive comments of the anonymous
reviewers, which have improved this manuscript.
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