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Energy 107 (2016) 131e140

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Energy
journal homepage: www.elsevier.com/locate/energy

Batch anaerobic co-digestion of OFMSW (organic fraction of municipal


solid waste), TWAS (thickened waste activated sludge) and RS (rice
straw): Inuence of TWAS and RS pretreatment and mixing ratio
Zaidun Naji Abudi a, c, Zhiquan Hu a, *, Na Sun a, Bo Xiao a, Nagham Rajaa b, c, Cuixia Liu a,
Dabin Guo d
a

School of Environmental Science and Engineering, Huazhong University of Science and Technology, Wuhan, 430074, PR China
School of Civil Engineering and Mechanics, Huazhong University of Science and Technology, Wuhan, 430074, PR China
Al-Mustansiryiah University, College of Engineering, Baghdad, Iraq
d
Safe Cleen Technologies Co. Ltd, Wuhan, 430074, PR China
b
c

a r t i c l e i n f o

a b s t r a c t

Article history:
Received 24 September 2015
Received in revised form
29 March 2016
Accepted 31 March 2016

The biochemical methane potential of co-digestion of OFMSW (organic fraction of municipal solid
waste), TWAS (thickened waste activated sludge) (thermal and thermo-alkaline pretreated) and RS (rice
straw) (NaOH and H2O2 pretreated) were investigated in this paper. The batch experiments were conducted at three different OFMSW/TWAS/RS (volume basis) ratios of 1:1.5:1.5, 1:0.5:0.5, and 3:0.5:0.5,
respectively. In addition, to predict the biogas yield and evaluate the kinetic parameters, modied
Gompertz model was introduced. A 3:0.5:0.5 ratio of OFMSW mixed with thermo-alkaline-treated TWAS
and H2O2-treated RS produced the highest biogas production (558.5 L/kgVSadded) and the highest VS
(volatile solids) removal efciency (76.9%) due to the synergistic effect. The modied Gompertz model
(R2: 0.868e0.998 and 0.910e0.999 for mono- and co-digestions, respectively) showed a good t to the
experimental results and the estimated parameters indicated that the pretreatments and co-digestion of
substrates markedly improved the biogas production rate.
2016 Elsevier Ltd. All rights reserved.

Keywords:
Anaerobic co-digestion
OFMSW (organic fraction of municipal solid
waste)
Thermal and thermo-alkaline pretreatment
NaOH and H2O2 pretreatment
Kinetic study

1. Introduction
The energy demand was estimated to be increased by a factor of
two or three during this century. This demand is currently being
met by coal and oil, which is depleting our resources and causing
many of the environmental problems [1]. Biogas, which is the main
product of anaerobic digestion process, has been regarded as a
promising alternative source of energy and it can be used for the
following applications: generation of heat or electricity from
burned biogas, liquefaction of biogas into methanol and chemical
feedstocks, compression of biogas to be used as a source of car fuel
similar to that of compressed natural gas, and purication of biogas
to be fed into gas distribution grids [2].
AD (anaerobic digestion) refers to a process where organic
matter is decomposed synergistically by a microbial consortium in
an oxygen free environment. AD provides not only an alternative

* Corresponding author. Tel.: 86 87557464; fax: 86 27 87557464.


E-mail address: huzq@hust.edu.cn (Z. Hu).
http://dx.doi.org/10.1016/j.energy.2016.03.141
0360-5442/ 2016 Elsevier Ltd. All rights reserved.

source of energy but also an alternative route to divert organic


wastes and reduce greenhouse gas emissions from landlls [3]. A
wide range of organic materials, such as municipal solid waste,
industrial organic waste, animal manure, and agricultural residues,
have been used as feedstocks in AD process.
OFMSW (organic fraction of municipal solid waste) is a common
name for heterogeneous waste mixtures from residential, commercial, partly industrial and urban areas. It is made up of different
organic and inorganic fractions such as food, vegetables, paper,
wood, plastics, glass, metals and other inert materials. Despite the
variability in its composition, the organic content constitutes the
highest percentage of the solid waste which can be broken down
into simpler compounds by anaerobic microorganisms [4]. Due to
its high VS (volatile solids), this waste is of particular interest for
A.D.
WAS (waste activated sludge) is the byproduct during wastewater treatment process. Large amounts of organics in wastewater
are converted to waste activated sludge during biological wastewater treatment [5]. The widely applied treatment for sludge stabilization is anaerobic digestion, which can reduce the sludge

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Z.N. Abudi et al. / Energy 107 (2016) 131e140

volume, generate methane gas, and yield a nutrient-rich nal


product [6]. However, the digestion efciency of WAS is largely
limited due to the relatively slow hydrolysis process, as WAS is
mainly composed of microbial cells within extracellular polymeric
substances, which presented physical barriers to direct anaerobic
degradation [7]. Many different pretreatment technologies have
been investigated to overcome these limitations, such as mechanical [8], ultrasonic [9], thermal and alkaline [10] treatment were
reported to improve the efciency of AD by disrupting sludge
membranes to release the intracellular nutrients. Most of the pretreatment studies showed enhanced digestion performance in
terms of sludge solubilisation followed by improved methane
production [11]. The main purposes of such pretreatment technologies are to increase the sCOD (soluble chemical oxygen demand) and reduce the particle size of the particulate matter.
Among these methods, alkaline pretreatment presents the
obvious advantages over others: a simple device, ease of operation,
and high methane conversion efciency. Zhang et al. [12] found
that the sludge pretreated at pH 10 for 8 days gave the highest
accumulative methane yield which was 3.5- and 3.1-fold of the
ultrasonic and thermal pretreated sludge, respectively. Recently,
this pretreatment has been combined with other sludge disintegration methods such as thermal treatment [13], ultrasound [14],
and microwave [15] to maximize the sludge biodegradability and/
or methane production.
China, which ranks rst in the world in crop straw residue
production, is estimated to produce over 800 million (tons/year) of
crop residues [16]. RS (rice straw), among these crops, represents
the largest portion and accounts for 32.3% of the total crop straw
output [17]. Most RS is being burned in the eld, which results in
severe environmental pollution such as greenhouse gases and nitrogen oxide [18]. So, it is necessary to nd environmentally
friendly alternatives to treatment and utilization of rice straw. RS
can be transformed into renewable energies, such as biogas and
biohydrogen, by anaerobic digestion [19,20]. However, the efciency of AD in treating agricultural straws is limited because some
fractions such as lignocelluloses in straw are difcult to degrade. To
improve the biodegradability, physical, chemical, and biological
pretreatments, such as size reduction, alkaline, and fungal pretreatment, have been investigated [21].
Compared with physical and biological methods, chemical
pretreatment methods, are mostly used because they are simple,
quick and effective for improving the biodegradation of complex
materials [22]. Many chemicals such as acid, alkali, and oxidizing
agent [20] have been studied as pretreatment agents. The most
commonly used alkali is sodium hydroxide. R. Chandra et al. [23]
reported that NaOH pretreated RS showed an increase of 132.0%
in biogas production and an increase of 123.9% in methane production relative to the untreated RS. One of the newest chemical
methods is hydrogen peroxide (H2O2) pretreatment. It is used
mostly for biomass delignication. Song et al. [19] showed that the
H2O2 treated RS experiment resulted in a methane yield of 88.0%
higher than that of untreated rice straw.
Co-digestion of various organic wastes for energy production
has aroused renewed interest recently. Co-digestion offers some
important advantages: dilution of potential toxic compounds;
improved balance of nutrients; synergistic effect of microorganisms; increased load of biodegradable organic matter and better
biogas yields [24]. Co-digestion of OFMSW and WAS or RS has been
reported previously [25,26]. However, the sludge and straws that
they used were raw ones without any pretreatment. This would
lead to poor biogas yield, limiting their practical application in large
scale.
So far, no studies were conducted on anaerobic co-digestion of
OFMSW, TWAS (thickened waste activated sludge) (untreated and

pretreated) and RS (untreated and pretreated). Therefore, the novel


concern of the current study is to investigate the effect of pretreating of TWAS and RS on anaerobic co-digestion and compare
the behavior of untreated and pretreated substrates for effective
biogas production. The objective of this work was to evaluate the
performance and synergistic effect of co-digestion of OFMSW with
thermal/NaOH-treated TWAS and NaOH/H2O2-treated RS under
mesophilic (37 1  C) fermentation conditions. Batch anaerobic
digestion tests, for this purpose, were performed in order to check
the BMP (biochemical methane potential) under different pretreatments and mixing ratios. Moreover, the biogas production
rate and specic biogas yield of single and mixing samples were
determined, and the difference between actual biogas yield and
simulated and calculated biogas yields from the co-digestion of
OFMSW, TWAS (untreated, thermal and thermo-NaOH pre-treatments) and RS (untreated, NaOH and H2O2 pre-treatments) was
then compared. Volatile solids removal efciency was selected to
reect the effects of pretreatments and anaerobic co-digestions.
Lastly, the kinetic model parameters of the batch experiment
were analyzed.
2. Material and methods
2.1. Feedstocks and inoculum
OFMSW, TWAS (thickened waste activated sludge) (untreated
and pre-treated) and RS (rice straw) (untreated and pre-treated)
were used in this study. TWAS and inoculums were collected
from the local MWWTP (Municipal Waste Water Treatment Plant).
RS was obtained from a rural area in Wuhan, China.
Because of real OFMSW has variable characteristics; therefore
prepared or model OFMSW was used to minimize compositional
variation. OFMSW was prepared in the lab with constituents which
simulate green bin waste or kitchen waste. OFMSW, which mainly
consisted of rice, vegetable and meats, was crushed with electrical
blender [27]. The crushed OFMSW was sealed in a plastic bag and
stored in a refrigerator at (4  C). The waste was allowed to reach
room temperature prior to the testing. TWAS (thickened waste
activated sludge) and inoculum were obtained from a full-scale
municipal wastewater treatment plant. Collected sludge and inoculum were stored at 4  C for subsequent experiments. RS (rice
straw) was obtained from a rural area in Wuhan, China. The RS was
completely dried in an oven at 105  C for more than 20 h. The dried
RS was ground to (<5 mm) particles by a hammer mill and then
used as the co-substrate.
2.2. TWAS pre-treatments
Two pretreatment methods-thermal and thermo-alkaline
treatments were selected from the preliminary study and literature review and applied to enhance AD of TWAS by partial
destruction of cells. TWAS thermo-alkaline pretreatment was carried out using NaOH which is known to be the alkaline agent with
the highest disintegration efcacy [11]. Thermal pretreatment was
conducted for 9 h at 70  C with a water bath. Thermo-alkaline
pretreatment was conducted at a condition of 90  C and pH 11
for 10 h. Alkaline was adjusted to pH 11 by 5 N NaOH [10]. A 500-mL
TWAS sample was mixed with NaOH in a 1-L beaker covered with
plastic wrap and agitated with a shaker for 10 min to completely
dissolve the NaOH. The mixture was then treated in a water bath at
90  C for 10 h with manual shaking for 1 min every hour. After
pretreatment, all treated sludge samples were adjusted to pH 7.0
and stored at 4  C before AD. The DS (degree of solubilisation),
which is dene as the evaluation indexes of the sludge disintegration degree reported by Appels et al. [28], of the organic

Z.N. Abudi et al. / Energy 107 (2016) 131e140

substances in the sludge was measured using sCOD (soluble


chemical oxygen demand). The degree of sludge disintegration was
calculated as the ratio of the increase in sCOD due to thermal and
thermo-alkaline treatments to the maximum possible sCOD increase (i.e., the difference between total COD (chemical oxygen
demand) and the sCOD prior to treatment) [11]:

degree of solublization%

sCODpretreated  sCODcontrol
TCODcontrol  sCODcontrol

Table 1
Experimental procedure.
Group no.

Treatment type

Treatment
symbol

OFMSW (mono-digestion)
TWAS (mono-digestion)
TWASthermal (mono-digestion)
TWASthermal-NaOH (mono-digestion)
R.S (mono-digestion)
R.SNaOH (mono-digestion)
R:SH2 O2 (mono-digestion)
OFMSW:TWASthermal:R.S (1:1.5:1.5)
OFMSW:TWASthermal:R.S (1:0.5:0.5)
OFMSW:TWASthermal:R.S (3:0.5:0.5)
OFMSW:TWAS:R.SNaOH (1:1.5:1.5)
OFMSW:TWAS:R.SNaOH (1:0.5:0.5)
OFMSW:TWAS:R.SNaOH (3:0.5:0.5)
OFMSW:TWASthermal:R.SNaOH (1:1.5:1.5)
OFMSW:TWASthermal:R.SNaOH (1:0.5:0.5)
OFMSW:TWASthermal:R.SNaOH (3:0.5:0.5)
OFMSW:TWASthermal-NaOH:R.SNaOH (1:1.5:1.5)
OFMSW:TWASthermal-NaOH:R.SNaOH (1:0.5:0.5)
OFMSW:TWASthermal-NaOH:R.SNaOH (3:0.5:0.5)
OFMSW:TWASthermal-NaOH:R:SH2 O2 (1:1.5:1.5)
OFMSW:TWASthermal-NaOH:R:SH2 O2 (1:0.5:0.5)
OFMSW:TWASthermal-NaOH:R:SH2 O2 (3:0.5:0.5)

A
B
C
D
E
F
G
H
I
J
K
L
M
N
O
P
Q
R
S
T
U
V

(1)

where sCODpretreated and sCODcontrol is the sCOD concentrations of


the treated and untreated sludge samples, respectively and TCODcontrol is the total chemical oxygen demand of the sludge before
pretreatments.

2.3. RS pre-treatments

Two types of chemical pretreatments were applied to rice


straw; (i) NaOH, and (ii) H2O2. Powdered NaOH (97.0% purity) of
0.75 g was added to 25.0 g of dried rice straw followed by
addition of water to maintain 5% total solids concentration. The
prepared substrates were kept in temperature controlled incubator for 5 days maintained at 37  C. The samples were daily
shaken thoroughly by hand to keep homogeneity of the substrates [23]. Second chemical treatment (H2O2) carried out by
using concentrations of 3% (w/w). Dried rice straw (100 g) was
soaked in the prepared 300 mL solutions contained in beakers,
yielding straw samples with 75% moisture. All prepared beakers
were enclosed with plastic lms, secured with a plastic ring, and
then stored at an ambient temperature of 25 2  C for 7 days.
After the pretreatment, the straws were dried in an electronic
oven at 80  C for 48 h, and then kept in a refrigerator for AD
experiments to investigate the effect of chemical treatments on
biogas yield [20].

133

were placed in a water bath shaker to provide continual homogeneous mixing of the mixtures at approximately 100 rpm and to
incubate the bottles at the mesophilic temperature of 37 1  C.
During the digestion period, biogas productions were determined
daily. After biogas production stopped, the digestates were nally
sampled to determine pH, TS, VS, VFA (volatile fatty acid), alkalinity
and total and soluble COD, in order to analyze the treatment
efciencies.
2.5. Analytical methods

2.4. Batch experimental setup


Batch anaerobic co-digestion was conducted to further examine
the effect of pretreatments of TWAS and RS on biogas production
from anaerobic co-digestion with OFMSW. OFMSW, TWAS (untreated and pre-treated), RS (untreated and pre-treated), and their
mixtures were separately examined, in mono-digestion or codigestion, respectively. The BMP (biochemical methane potential)
assays were conducted according to the procedures described in
the literature [29]. The assays were carried out in six groups
(Table 1); the rst group was mono-digestion of substrates
(OFMSW, TWAS (untreated and pre-treated) and RS (untreated and
pre-treated)). Other assays, from group 2 to 6, were conducted by
co-digestion of OFMSW/TWAS/RS with different mixing ratios
(1:1.5:1.5, 1:0.5:0.5, and 3:0.5:0.5, as volume basis). Forty six
250 mL BMP bottles were set up in duplicates with a working
volume of 180 mL. The TS (total solids) content in each reactor was
adjusted to 5% and the working volume was composed of 80%
substrate and 20% inoculum. Before seeding, the inoculum was
placed in an incubator for 10 d until biogas production stopped to
minimize the contribution from the remaining organic materials
contained in the inoculum. After adding the designed amounts of
inoculum and substrate, each bottle was lled with distilled water
to reach the desired volume. Assays with inoculum alone were also
used as the control samples. The initial pH adjusts at 7.0 0.1 for
the mixed liquor in each digester by using 1 M HCl or 1 M NaOH
[24].
After adding the substrates, the bottles were purged with nitrogen for 2e5 min to eliminate oxygen. The bottles were then
immediately capped tightly with rubber stoppers. The bottles then

All analyses were duplicated, and the results given are mean
values. The TS (total solids), VS (volatile solids), and TCOD (total
chemical oxygen demand) contents of OFMSW, TWAS, RS and
inoculum and digestate were determined according to the Standard
Methods [30]. The pH was determined with a pHS-25C pH meter
made by Shanghai Precision & Scientic Instrument Co., Ltd. The
carbon and nitrogen analysis was conducted using a Vario EL
(element analyzer) made by Elementar Analysensysteme GmbH.
The cellulose, hemicellulose and lignin were determined according
to the method of Van Soest [31].
Biogas production volume was measured daily by the water
displacement method and transferred to the standard condition.
Assay bottles (500 mL volume) were removed from the incubator
and allowed to cool to room temperature prior to biogas volume
measurement, after that connect it to a 1-L gas collection glass
bottle and a 250-mL liquid collection cylinder, and then an equivalent volume of liquid to the produced biogas was displaced to the
liquid collection cylinder. Biogas produced from the inoculum was
subtracted from the sample assays. The CH4 gas content was
analyzed via gas chromatography (SP-2100, China) equipped with a
TCD (thermal conductivity detector) and a packed column. For the
calibration, standard gases (H2, O2, N2, CH4, CO2: purity >99.9%)
were used. The temperature of injector port, column and detector
was increased from 70  C, 50  C and 70  C to 120  C, 95  C and
150  C, respectively. Argon was used as the carrier gas at a ow rate
of 40 mL/min.
Samples from substrates and reactors were ltered through a
ltration membrane with a pore size of 0.45 mm, after which they
were diluted 10 times with distilled water to determine VFA,

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Z.N. Abudi et al. / Energy 107 (2016) 131e140

alkalinity, and the sCOD (soluble chemical oxygen demand) [32].


Total VFA and alkalinity were determined through a two-step
titration method [33]. SCOD was analyzed in accordance with the
Standard Methods [30]. The biogas yield of each substrate and
mixture at the end of each test was calculated by dividing the cumulative gas volume by the mass of VS in the feedstock loaded into
the reactors at start-up.
To evaluate the effect of co-digestion, SBY (simulated biogas
yield) of the mixtures was introduced. SBY was calculated based on
the weighted average of the biogas yield from each of the individual
single substrates and the portion of each waste co-digested in the
assay. If there is no effect of co-digestion the cumulative biogas
yield as measured for the particular mixture should be the same as
SBY value, as shown Eq. (2) [34]

SBYi BYOFMSW;mono;i  Y1 % BYTWAS;mono;i  Y2 %


BYRS;mono;i  Y3 %

The cumulative biogas production curves were recorded over


the digestion time of the batch experiments and described using
the modied Gompertz equation as follows [36]:


Gt Gmax exp



Rmax e
 exp
l  t 1
Gmax

(5)

where G(t) is the cumulative biogas yield at time t (mL/g VSadded);


Gmax is the biogas potential maximum production (mL/g VSadded);
Rmax is the maximum biogas production rate (mL/g VS-d); l is the
lag phase (d); t is the duration of the assay (d); and e is the
exp(1) 2.7183.
3. Results and discussion

(2)
3.1. Characteristics of feedstocks and inoculum

where i the digestion time (d); SBYi the simulate biogas yield of
mixture at the ith day (mL/g VSadded); BYOFMSW;mono;i biogas yield
of OFMSW at the ith day (mL/g VSadded); Y1% the percentage of
OFMSW in mixture (%); BYTWAS;mono;i biogas yield of TWAS at the
ith day (mL/g VSadded); Y2% the percentage of TWAS in mixture
(%), BYRS;mono;i biogas yield of RS at the ith day (mL/g VSadded);
Y3% the percentage of RS in mixture (%).
VS removal rate during the batch test was calculated according
to the following equation [35]

VSremoval

2.6. Kinetic model

F I  a  I  b
 100%
F

(3)

where F VSfeed added to reactor (g); I VSinoculums added to


reactor (g); a calculated VS removal of feed plus inoculums based
on total initial and nal VS present in the reactor (%); b calculated
VS removal of inoculum in blank reactor (%). To acquire the simulated VS removal for the co-digestion system, the following equation was used by modifying the main parameters of Eq. (2):

SVSi VSOFMSW;mono;i  Y1 % VSTWAS;mono;i  Y2 %


VSRS;mono;i  Y3 %

(4)

where i the digestion time (d); SVSi the simulate volatile solid
removal of mixture at the ith day (%); VSOFMSW;mono;i volatile solid
removal of OFMSW at the ith day (%); Y1% the percentage of
OFMSW in mixture (%); VSTWAS;mono;i volatile solid removal of
TWAS at the ith day (%); Y2% the percentage of TWAS in mixture
(%), VSRS;mono;i volatile solid removal of RS at the ith day (%);
Y3% the percentage of RS in mixture (%).

The results (pH, TS, VS, TCOD, sCOD, alk, TC (total carbon) and TN
(total nitrogen)) of the feedstocks (OFMSW, TWAS, RS and inoculum) characterization are summarized in Table 2. The highest TS
and VS percentages (92.6% and 70.4%, respectively), was for the RS
(rice straw), followed by OFMSW (23.3% and 20.2%, respectively),
and TWAS (14.2% and 6.7%, respectively). The inoculum had the
lowest TS and VS percentage values (2.3% and 1.4%, respectively).
The pH of OFMSW was the lowest (3.5), and inoculum had the
highest pH (6.5), followed by TWAS and RS (6.4 and 6.2,
respectively).
3.2. Solubilisation effects of TWAS pretreatments
A signicant increase in sCOD was observed in pretreatments
(thermal and thermo e alkaline), with SD (solubilisation degree)
values (36.9% and 31.7%), respectively. The sCOD to TCOD ratio of
34.6% in raw TWAS increased correspondingly to 63.6% and 68.1% in
the pretreated TWAS, respectively. These results indicate that the
particulate organic substances in TWAS were effectively solubilized
by thermal and thermo-alkaline treatments. SCOD released from
sludge solids, although not wholly biodegradable, provides an
additional amount of easily utilizable substrate for microbial
growth, reportedly leading to an enhanced sludge digestibility in
AD [37]. Biogas production increased in all pretreatments by 37.6
and 51.2% compared with the untreated control (262.0, 287.8, and
190.4 L/kgVSadded for TWASthermal, TWASthermo-alkaline, and TWASuntreated), respectively, indicating that the pretreatment improved
the anaerobic biodegradability of sludge. The observed increase in
biogas production above indicates that the enhanced TWAS
degradation was directly translated into enhanced biogas
production.

Table 2
Characteristics of feedstocks and inoculum.
Parameters

OFMSW

TWAS

RS

Inoculum

pH
T.S (%)
V.S (%)
V.S/T.S
TCOD (mg/l)
sCOD (mg/l)
sCOD/TCOD
alk (mg/l CaCO3)
Total carbon (%/TS)
Total nitrogen (%/TS)

3.5 0.04
23.3 0.34
20.2 0.26
88.5
210,667 3581
110,050 1610
52.2
500 12
45.6 0.7
2.1 0.2

6.4 0.00
14.2 0.16
6.7 0.09
47.4
37,040 1332
12,800 750
34.6
1500 21
35.4 1.3
5.6 0.15

6.2 0.02
92.6 0.31
70.4 0.22
76.0
ND
ND
ND
ND
40.9 1.1
0.7 0.04

6.5 0.05
2.3 0.39
1.4 0.35
60.0
19,040 1351
5600 452
29.4
667 14
ND
ND

Note: ND, not determined.

Z.N. Abudi et al. / Energy 107 (2016) 131e140


Table 3
Cellulose, hemicellulose and lignin contents (%, dry basis) of rice straw after
chemical pretreatment.

Cellulose (%)
Hemicellulose (%)
Lignin (%)

Untreated

H2O2

NaOH

38.4 1.4
28.2 1.2
7.2 0.4

32.4 1.3
16.6 1.1
6.7 0.2

34.4 1.5
19.1 0.9
5.6 0.3

3.3. Effect of pretreatments on the main compositions of rice straw


As the main carbon source in agriculture waste for anaerobic
microorganisms, hemicellulose, cellulose, and lignin are the main
compositions of rice straw, which account for 74% of the total dry
matter of rice straw. Biogas production is greatly affected by the
availability and digestibility of cellulose and hemicellulose as well
as the association of lignin with the carbohydrates. The hemicelluloses, cellulose, and lignin contents (based on initial dry

135

matter) in RS pretreated with NaOH and H2O2 were shown in


Table 3. Contents of the cellulose and hemicellulose in RS
remarkably decreased in all the treatments compared with the
untreated. These results are similar with previous studies, in
which 30%e60% of cellulose and hemicellulose were broken
down in the alkaline (NaOH)-treated materials [38]. Some researchers showed that pretreatments signicantly affected the
solubilisation of the main components of agricultural wastes, in
the present study, H2O2 pretreatment led to considerable reductions in cellulose (15.7%), hemicellulose (40.9%) and lignin
(7.0%). While for NaOH pretreatment, reductions in the above
three components were 10.5%, 32.1%, and 21.9%, respectively. The
results showed that more hemicellulose was solubilized as
compared to lignin and cellulose, indicating that NaOH and H2O2
are particularly effective in the decomposition of hemicellulose in
rice straw. These results are consistent with that of previous
studies where hemicellulose was completely decomposed while
only 17.1% of the lignin was decomposed in rice straw after 8%
NaOH pretreatment [39].

Fig. 1. Daily biogas yields during anaerobic digestion of OFMSW, TWAS (untreated and treated), and RS (untreated and treated), in mono- and co-digestion.

136

Z.N. Abudi et al. / Energy 107 (2016) 131e140

3.4. Biogas production


The daily biogas yields of different treatments are shown in
Fig. 1. The biogas production processes ran for about 55 days. All the
assays were nished when the biogas production was below 5% of
the total cumulative production [40]. Biogas production started
immediately from the rst day for all digestion tests. For group one,
treatment A, one peak of the daily biogas yield was observed, which
occurred on the rst day (138.2 L/kg VS-d), due to higher sCOD
content, which could be rapidly biodegraded in the rst day. The
peak values of daily biogas yield for treatments C and D were 16.2%
and 42.9% higher than that of treatment B. While for treatments F
and G, their peak values were 189.2% and 51.8% higher than E's peak
daily biogas yield. These results indicate that the enhanced TWAS
and RS degradation were directly translated into enhanced biogas
production.
For the other groups (2e6), and for the rst mixing ratio
(1:1.5:1.5), the highest biogas production rate (38.7 L/kg VS-d) was
obtained at T treatment, which was (1.5e1.8)-fold higher than
those of the treatments H, K, N, and Q. The highest biogas

production rate (89.1 L/kg VS-d), for (1:0.5:0.5) mixing ratio, was
obtained at L treatment, which was (1.2e4.1)-fold higher than
those of I, O, R, and U treatments. At mixing ratio of 3:0.5:0.5, V
treatment produced the highest biogas production (150.3 L/kg VSd), which was 1.1e2.7 fold higher than those of J, M, P, and S
treatments. However, biogas production rate dropped after the
peak for the digestion system with (89.1 L/kg VS-d), and no biogas
was produced with the treatment L from day 4 to 11, indicating that
an apparent severe inhibition occurred. The inhibition was probably caused by the higher digestibility of substrates, leading to
overproduction of VFAs that inhibited the methanogenesis process
[41]. Then after about 8 days of self-recovery, the system started
again to produce biogas. Treatments J, O, R, S, T, U, and V also had
similar biogas production processes.
From Fig. 2, it can also be seen that at the end of the digestion
process, the total biogas yields were 214.5, 190.4, 262.0, 287.8,
229.9, 391.1, and 319.8 L/kgVSadded for the group 1, respectively. As
could be seen from Fig. 2, the cumulative biogas production of the
TWAS anaerobic digestion pretreated by two methods was higher
than that of the TWAS without pretreatment obviously. Ray had

Fig. 2. Cumulative biogas yields during anaerobic digestion of OFMSW, TWAS (untreated and treated), and RS (untreated and treated), in mono- and co-digestion.

Z.N. Abudi et al. / Energy 107 (2016) 131e140

pointed out that pretreatment with alkaline increased biogas production by 29%e112% over the control sludge [42]. The cumulative
biogas yield of the treatment B (TWASuntreated) was only 187.4 L/
kgVSadded after 55 days anaerobic digestion, however, the cumulative biogas yield of TWAS after thermal and thermo-alkaline
pretreatments (treatments C and D) were 262.0 L/kgVSadded and
287.8 L/kgVSadded, respectively. Meanwhile, the biogas production
increased by 39.8% and 53.6% compared to the control, respectively.
For the digestion of RS, compared to the untreated rice straw
(treatment E), the NaOH and H2O2 pretreatments (treatments F and
G) achieved 71.6% and 41.4% more biogas yield, respectively (Fig. 2).
The results proved that NaOH and H2O2 pretreatments were efcient approaches to improve biogas production from rice straw. The
increase of biogas yield was attributed to the enhanced biodegradability of rice straw after NaOH and H2O2 pretreatments, which
made more substrates accessible to be digested by anaerobic
microorganisms.
For second to sixth groups under mixing ratio of 1:1.5:1.5, the
highest total biogas yield (386.5 L/kgVSadded) was achieved in T
treatment. With respect to mixing ratio of 1:0.5:0.5, the highest
biogas yield (472.1 L/kgVSadded) was observed in U treatment.
While for mixing ratio of 3:0.5:0.5, V treatment had the highest
biogas yield (558.5 L/kgVSadded).
Approximately 52.0e95.5% and 19.0e82.4% of the total biogas
yields were obtained after rst 25 days of digestion, for mono- and
co-digestion, respectively. The percentage of cumulative biogas to
the total was used to indicate the completeness of biogasication.
From the percentages of cumulative biogas yield to the total, it can
be seen that treatments B, A, N and Q exhibited faster in biogas
production than other treatments.
The observed and simulated cumulative biogas yields from codigestion of OFMSW/TWAS(untreated and treated)/RS(untreated and
treated) were shown in Table 4. Compared with mono-digestion of
group 1, groups 2e6 were all enhanced in the biogas yields.
Moreover, the observed cumulative biogas yields in co-digestion
were much higher (1.2e2.4times) than those of simulated results
(Table 4).
Table 4 summarizes the analyzes for co-digestion mixtures of
OFMSW, TWAS(untreated and treated) and RS(untreated and treated),
depicting the differences between the biogas yields from co-

137

digestion samples and the SBYs calculated from mono-digestion


biogas yields. The data suggest, however, that the co-digestion of
OFMSW with TWAS(untreated and treated) and RS(untreated and treated) is
synergistic, since biogas yields of groups 2e6 are 44.6e143.4%,
32.6e135.4%, 23.6e128.3%, 22.5e129.8%, and 38.2e140.0%, higher
than their SBY, respectively. Synergistic effect may arise from the
fact that all the OFMSW/TWAS/RS mixtures under different mixing
ratios of 1:1.5:1.5, 1:0.5:0.5, and 3:0.5:0.5 gave better C/N ratios
(30.35e26.12), which were in the optimal range for anaerobic
digestion (15e30) [1,25]. Thus, the more balanced anaerobic environment has likely resulted in an increased biogas production of
mixed biomass. Hence, improving the C/N ratio seems to be the
most important positive effect in co-digestion process [25].
3.5. Volatile solids removal
One of the most useful parameters for evaluating the efciency
of anaerobic digestion is the reduction in VS (volatile solids). As
shown in Fig. 3, treatment S obtained the highest rate of VS
destruction at 76.9%, while treatment B had the lowest at 34.5%.
Similarly, Takashima M. [43] reported only 30e40% of the organic
matter content in waste active sludge was degraded in mesophilic
temperature conditions. With respect to treatments C and D, as
comparison with B treatment, the VS removal efciency was
increased by 10.2% and 28.7%, respectively. These results are
consistent with previous studies, in which VS removal rates of
TWAS pretreated by different methods were: thermal pretreatment
43.7%, thermal-alkaline 46.2% [10]. VS reduction of treatment A in
this experiment (43.3%) was relatively lower than the VS reduction
lez et al. [44], but Cabbai et al.
(65.2%) achieved by L. Martn-Gonza
[45] presented a similar VS reduction of 33%. The treatment E'VS
reduction in this study (58%) was higher than the VS reduction
(51.5%) achieved by Ye et al. [34]. Treatments F and G, as shown in
Fig. 3, showed an increase of 6.0% and 13.1% in VS removal rates, as
compared to treatment E. The observed increase in VS reduction
above indicates that the enhanced TWAS and RS degradation was
directly translated into enhanced VS reduction.
Based on proportions of OFMSW, TWAS(untreated and treated) and
RS(untreated and treated) in the mixtures and the VS removal rates of
OFMSW, TWAS(untreated and treated) and RS(untreated and treated), the

Table 4
Synergistic effect evaluation of co-digestion of OFMSW, TWAS and RS.
Group no.

Treatment

BY

SBY

(L/kgVS)

(L/kgVS)

A
B
C
D
E
F
G
H
I
J
K
L
M
N
O
P
Q
R
S
T
U
V

214.5
190.4
262.0
287.8
229.9
391.1
319.8
339.9
444.3
530.3
354.7
450.0
538.3
365.0
456.7
543.3
373.9
466.6
554.4
386.5
472.1
558.5

e
e
e
e
e
e
e
238.1
230.2
222.4
271.7
252.6
233.6
298.5
270.5
242.5
308.2
277.0
245.8
281.5
259.2
236.8

Differential (BY-SBY)

Increasing rate of biogas yield (%)

Synergistic effect

e
e
e
e
e
e
e
101.8
214.0
307.9
83.0
197.4
304.8
66.5
186.2
300.7
65.7
189.6
308.6
105.0
212.9
321.7

e
e
e
e
e
e
e
42.7
93.0
138.4
30.5
78.1
130.5
22.3
68.8
124.0
21.3
68.5
125.6
37.3
82.1
135.8

e
e
e
e
e
e
e
Synergistic
Synergistic
Synergistic
Synergistic
Synergistic
Synergistic
Synergistic
Synergistic
Synergistic
Synergistic
Synergistic
Synergistic
Synergistic
Synergistic
Synergistic

138

Z.N. Abudi et al. / Energy 107 (2016) 131e140

Fig. 3. Volatile solids removal efciency. Error bars represent standard deviation.

simulated VS removal rates for the 2nd to 6th groups were shown
in Fig. 3. The actual VS removal rates for the co-digestion was
increased by 5.2e64.7%, 11.0e68.8%, 9.6e67.2%, 8.2e66.2%, and
8.7e67.1% more than their simulated values, respectively (Fig. 3).

3.6. Kinetic study results


Tables 5 and 6 summarize the results of a kinetic study for
OFMSW, TWAS(untreated and treated), and RS(untreated and treated) in
mono- and co-digestion, by using the modied Gompertz model.
From Tables 5 and 6, Rmax (the maximum biogas production rate)
values estimated by modied Gompertz model, for group 1 were
27.7, 11.9, 14.9, 15.2, 7.2, 13.3, and 11.2 L/kg VS-d. These tables also
showed that the Rmax was improved for second to sixth group, than
rst group. This reected that co-digestion of OFMSW, TWAS(untreated and treated), and RS(untreated and treated) signicantly accelerated
the mixing substrates' conversion rate.

The other important indicator of substrate biodegradability and


utilization rate was the digestion time [24]. The technical digestion
time (T90) is dened as the time taken to achieve 90% of maximum
cumulative biogas production [35]. The effective biogas production
period (Tef) was calculated by subtracting the lag time (l) from T90
(Tables 5 and 6). The Tef value for B treatment was found to be lower
than those for other treatments in rst group, while the Tef was
increased in the other treatments. One possible reason for the
increased Tef under co-digestion conditions could be the VFA's inhibition to methanogens due to OFMSW's rapid acidication. Based
on the parameters obtained from the model, the high biogas production rate and short effective biogas production time were obtained in the systems of co-digestion of OFMSW, TWAS(untreated and
treated), and RS(untreated and treated).
As shown in Tables 5 and 6, the difference between the predicted and measured biogas yields in the modied Gompertz
model were 0.00e6.63%, 4.58e11.41%, 0.12e13.73%, 0.40e5.60%,
1.75e11.79% and 2.32e5.36%, respectively. The correlation coefcients R2 values fell within the ranges of 0.868e0.998 and
0.910e0.999 for mono- and co-digestions, respectively.
3.7. Economic evaluation of pretreatment
To investigate the economic feasibility of the suggested pretreatment process, a simple economic analysis (Table 7) for 1 ton of
each raw material with consideration of chemicals and energy costs
used in pretreatments was conducted. The electrical energy
required for TWAS thermal and thermo-alkaline pretreatments and
RS heating during NaOH pretreatments was calculated by following
the method described in Sambusiti et al. [21]. Economic calculations were conducted for different treatments in mono-digestion
and three best co-digestion (V, S, and P). Table 7 also shows the
assessment of the methane conversation to heat and electric energy by CHP (combined heat and power) for TWAS and RS in monoand co-digestions with different pretreatments. CHP yields were
considered to be 41% for heat and 40% for electricity [21].
According to the data shown in Table 7, although all pretreatment conditions signicantly improved biogas production relative
to the untreated, all mono-digestion processes produced less

Table 5
Model parameters of the modify Gompertz model for (A, B, C, D, E, F, G, H, I, J, K, L, and M) treatments.

Correlation coefcient R2
Rmax (L/kg VS-d)
l (d)
T90 (d)
Tef (d)
Predicted biogas yield (L/kg VS)
Measure biogas yield (L/kg VS)
Difference between measured
and predicted biogas yield (%)

0.868
27.7
0.00
11.00
11.00
214.5
214.5
0.00

0.998
11.9
2.16
21.00
18.84
190.2
190.4
0.08

0.998
14.9
5.60
29.00
23.40
261.3
262.0
0.28

0.997
15.2
4.61
32.00
27.39
286.7
287.8
0.40

0.996
7.2
6.03
42.00
35.97
215.6
229.9
6.63

0.998
13.3
3.12
38.00
34.88
377.6
391.1
3.58

0.994
11.2
8.20
39.00
30.80
304.1
319.8
5.17

0.992
11.0
3.37
38.00
34.63
324.9
339.9
4.58

0.991
17.0
17.62
49.00
31.38
404.7
444.3
9.79

0.969
25.5
25.36
51.00
25.64
475.9
530.3
11.41

0.998
14.0
3.94
33.00
29.06
347.9
354.7
1.94

0.959
10.2
0.53
44.00
43.47
395.7
450.0
13.73

0.947
30.7
0.00
35.00
35.00
537.7
538.3
0.12

Table 6
Model parameters of the modify Gompertz model for (N, O, P, Q, R, S, T, U, V, W, X, and Y) treatments.

Correlation coefcient R2
Rmax (L/kg VS-d)
l (d)
T90 (d)
Tef (d)
Predicted biogas yield (L/kg VS)
Measure biogas yield (L/kg VS)
Difference between measured and predicted biogas yield (%)

0.998
13.9
3.37
35.00
31.63
357.2
365.0
2.18

0.994
15.9
8.93
43.00
34.07
432.5
456.7
5.60

0.910
26.1
0.00
37.00
37.00
541.1
543.3
0.40

0.999
14.2
1.17
35.00
33.83
367.5
373.9
1.75

0.987
14.7
4.09
38.00
33.91
442.2
466.6
5.53

0.932
13.0
0.00
47.00
47.00
495.9
554.4
11.79

0.988
14.3
9.44
43.00
33.56
369.2
386.5
4.68

0.976
13.7
0.00
39.00
39.00
448.1
472.1
5.36

0.949
19.6
0.00
37.00
37.00
545.9
558.5
2.32

All results are shown for per 1 ton of raw materials.


CH4 increase represents the difference between pretreated and untreated substrates for mono-digestion, while for co-digestion; it represents the average differences between co-digestion and base line (mono-digestion);
methane percent was assumed 65% of biogas.
c
CHP yields were considered to be 41% for heat and 40% for electricity.
d
The price of chemicals was collected according to market price.
e
Electricity cost is calculated according to Hubei power grid electricity sales price, China.

188.6
223.5
165.5
0.30
0.04
5.1
8.8
3.8
Treatment V
Treatment S
Treatment P

RS

49.4
36.6
456.0
63.2
10.8
4.6
20.6
28.1
46.5
25.9
92.9
67.1
67.6
176.3
239.9
396.9
221.4
793.3
572.8
577.6
172
234
387.2
216
773.9
558.9
563.6
43.0
58.5
96.8
54.0
193.5
139.7
140.9
1045.0
1509.0
278.7

Thermal @ 70  C
NaOH @ 90  C
NaOH @ 37  C
H2O2 @25  C
OFMSW:TWAS(NaOH @ 90  C):RS(H2O2); (3:0.5:0.5)
OFMSW:TWAS(NaOH @ 90  C):RS(NaOH); (3:0.5:0.5)
OFMSW:TWAS(Thermal):RS(NaOH); (3:0.5:0.5)
TWAS

40.5
30.0

NaOH
(kg)
Pretreatment
Substrate

Table 7
Economic analysis of different pretreatment.a

22.6
26.8
19.9

125.4
230.5
70.0
456.0
85.8
37.6
24.4
125.4
181.1
33.4

104.8
202.4
23.6
430.1
7.1
29.5
43.2

Total
treatment
cost ($)
Heat from
CHPc (kWh)
CH4 increaseb
(m3)
H2O2
(m3)

Thermal
(kWh)

Electricity from
CHPc (kWh)

Electricity
energy
gain ($)

Chemical
costd ($)

Treatment
electricity
coste ($)

Extra net
gain ($)

Z.N. Abudi et al. / Energy 107 (2016) 131e140

139

energy in the form of biogas than the amount of energy consumed


for substrates pretreatment; therefore, the extra net gains from
these processes are negative. On the contrary, in the co-digestion
processes the extra net gains obtained from different treatments
are all positive. Among these three co-digestion treatments, the
extra net gain of treatment P is much higher than those of treatments V and S (Table 7), which can be attributed to lower pretreatment cost used in this process. All co-digestion treatments are
economically feasible when compared to mono-digestion with net
gain of $7.1e43.2/ton of substrates. Therefore, this study provides
meaningful insight for exploring efcient pretreatment and codigestions strategies to stabilize and enhance anaerobic digestion
performance for practical application.
4. Conclusions
Co-digestion of OFMSW, TWAS (pretreated by thermal and
thermo-alkaline) and RS (pretreated by NaOH and H2O2) were
investigated in this study. The pretreatments improved biogas yield
of TWAS and RS by (37.6% and 51.2%) and (70.1% and 39.1%),
respectively. The highest biogas yield and VS removal fraction
(558.5 L/kgVSadded and 79.8%) were achieved from co-digestion of
OFMSW, TWASthermo-alkaline and RSH2 O2 at mixing ratio of 3:0.5:0.5.
The parameters obtained from the modied Gompertz model
indicated that the co-digestion of OFMSW, TWAS(untreated and treated),
and RS(untreated and treated) markedly improved the biogas production
rate.
Acknowledgments
The authors would like to acknowledge the nancial supports of
Iraqi scholarship foundation from Ministry of Higher Education and
Scientic Research of Iraq, Fundamental Research Funds for the
Central Universities (2015TS113), Wuhan International Science and
technology cooperation project (No. 2015030809020369) and SRF
(No. 20141865) for ROCS, SEM, China. We thank to the Analytical
and Testing Center of Huazhong University of Science and Technology (HUST), Wuhan, P.R. China for carrying out the analyses of
biomass samples.
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