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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
132
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)
2.3. RS pre-treatments
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
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,
134
Gt Gmax exp
Rmax e
exp
l t 1
Gmax
(5)
(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
F I a I b
100%
F
(3)
(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
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
135
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
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.
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
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)
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
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).
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
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 ($)
139
140
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