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Department of Chemical and Process Engineering, Universiti Kebangsaan Malaysia, 43600 UKM Bangi, Selangor,
Malaysia
b
Fuel Cell Institute, Universiti Kebangsaan Malaysia, 43600 UKM Bangi, Selangor, Malaysia
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abstract
Article history:
Many researchers have reported on the end products of the anaerobic digestion process as
biogas and methane but the useful intermediate products in the anaerobic digester
10 June 2015
substitute for fossil fuels with a variety of fuel applications and advantages with regard to
the environment, the economy, and consumers. Thus the main objective of this study is to
Keywords:
study was conducted in a room temperature, lab-scale reactor with a fixed retention time.
Methanol
Animal waste
observed that, banana peel (61.51 wt.%) and boiled rice (81.25 wt.%) substrates with cow
Agriculture waste
dung inoculum have the greatest potential for bio-methanol production via anaerobic co-
Anaerobic digestion
digestion. This study proves that the methanol exists as intermediate product of anaerobic
Intermediate product
co-digestion. Finally, this study concludes that by enhancing the production of methanol at
intermediate phase can reduce the production of methane gas.
Copyright 2015, Hydrogen Energy Publications, LLC. Published by Elsevier Ltd. All rights
reserved.
Introduction
Fossil fuels have become an important source of energy in the
last 20 years and account for 80.9% of the total world energy
supply [1]. However, fossil fuel use is responsible for the
emission of atmospheric pollutants, including greenhouse
gases [2]. In Malaysia, population and economic growth as
well as the increasing demand for energy have triggered a
* Corresponding author. Department of Chemical and Process Engineering, Universiti Kebangsaan Malaysia, 43600 UKM Bangi,
Selangor, Malaysia. Tel.: 60 389216422; fax: 60 389216148.
E-mail address: ctie@vlsi.eng.ukm.my (S.K. Kamarudin).
http://dx.doi.org/10.1016/j.ijhydene.2015.06.072
0360-3199/Copyright 2015, Hydrogen Energy Publications, LLC. Published by Elsevier Ltd. All rights reserved.
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Methodology
Pre-treatment and preparation of samples
The sample pre-treatment process was divided into two subprocesses: the drying process and the grinding process.
Table 1 shows the bio-solids that were studied in this
research. All samples were dried at 40 C for 2 days using an
oven (model Froilabo AC240, France) to reduce the moisture
content in the samples. The samples were ground using an
electrical kitchen blender (Pensonic PB-323, Japan) to reduce
the size of the particles and facilitate the digestion process. All
of the various mixtures of bio-solid samples were generated as
shown in Table 1 at a 1:1 ratio of bio-solid to distilled water
and stored at 4 C until used. Livestock wastes, including cow
dung, chicken manure, and goat dung, acted as an inoculum
for the anaerobic digestion process.
Reactor design
The laboratory-scale reactor consisted of a 500 mL Erlenmeyer
flask sealed with a rubber stopper. The reactor was sealed
with a two-channel plastic tube as the point of sample
collection and biogas collection. The biogas was collected and
measured using the water displacement method.
Pineapple peels
Spinach waste
Sugarcane bagasse
Papaya peel
Resources
Livestock farm, Bangi, Selangor,
Malaysia
Livestock farm, Salak Tinggi,
Selangor, Malaysia
Livestock farm, Banting, Selangor,
Malaysia
Market, Bangi, Selangor, Malaysia
Market, Bangi, Selangor, Malaysia
UKM campus, Bangi, Selangor,
Malaysia
UKM campus, Bangi, Selangor,
Malaysia
Restaurant, Bangi, Selangor,
Malaysia
Section 16, Shah Alam, Malaysia
Section 16, Shah Alam, Malaysia
Section 16, Shah Alam, Malaysia
Section 16, Shah Alam, Malaysia
Analytical methods
Proximate analysis was performed to determine total solids,
volatile matter, moisture content, ash content and fixed carbon of the bio-solids based on ASTM E1759-08 [32], ASTM E89788 [33], ASTM E949-88 [34], ASTM E830-87 [35] and ASTM
D5681-98a [36], respectively. Elemental (CHNSeO) analysis
(ThermoFinnigan, model EA1112, Italy) was used to determine
the elemental composition of the samples, according to the
manufacturer's standard procedure. The samples were
analyzed at the beginning and end of the experiment to
determine the ratio of carbon to nitrogen (C/N). The liquid
sample in the reactor was analyzed using HPLC (model Agilent
1200, USA). A mobile phase of 0.02 M H2SO4 and a stationary
phase of SaX were used. A refractive index detector at a
temperature of 30 C and with mobile phase velocity of
0.6 mL min1 was used.
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HRT (days)
Experiment 1
28
28
28
28
28
42
42
42
42
42
44
14
14
14
14
14
14
Experiment 2
Experiment 3
Experiment 4
Sample collection
Composition of feedstock
7 days interval
4 days interval
Accumulation in reactor for 2 weeks
corn stover
banana peel
boiled rice
grass
leaf
Ash (wt.%)
ND
61.76
86.83
60.44
11.92
12.90
13.33
38.32
19.17
5.34
12.41
5.26
34.22
37.43
63.13
48.84
50.84
64.90
66.79
59.49
53.04
91.02
61.17
92.56
0.51
0.33
1.00
0.05
1.82
0.94
93.57
84.11
93.57
51.16
49.16
35.10
33.21
40.51
49.96
8.98
66.13
7.44
1.71
2.36
2.75
2.86
2.62
2.42
17.90
12.95
15.57
46.62
48.15
61.15
63.88
55.05
49.68
7.78
2.94
14.78
ND Not determined.
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corn husk
banana peel
grass
boiled rice
leaves
Carbon, C
Hydrogen, H
Nitrogen, N
Oxygen, O
C/N ratio
6.63
6.34
8.96
6.04
6.63
12.83
8.98
9.30
8.14
6.34
25.62
36.16
21.93
20.79
6.45
2.94
13.59
6.03
3.26
9.03
10.68
9.17
9.73
9.03
e
7.43
8.21
9.50
4.31
4.15
5.89
7.77
3.69
7.78
3.69
9.91
2.97
2.50
1.89
2.14
2.26
3.12
1.89
2.55
1.97
2.21
1.91
2.65
4.23
2.35
1.52
2.57
2.34
2.57
2.32
1.73
1.89
82.45
80.85
79.61
81.13
82.45
84.62
81.61
80.30
80.45
86.70
66.00
55.59
68.78
90.8
83.43
90.8
74.18
89.27
92.35
3.51
2.96
3.96
1.94
3.51
5.04
4.55
4.22
4.26
2.39
6.18
15.39
14.43
8.09
2.76
1.14
5.86
3.49
1.72
Bio-methanol production
The efficiency of the anaerobic digestion process was evaluated in terms of the bio-methanol yield. The methanol percentages and concentrations in the product were determined
by analytical high-performance liquid chromatography. The
standard
retention
time
of
methanol
was
(3.265e3.289) 0.05 min Fig. 2 displays the bio-methanol yield
from Experiment 1. It was observed that the bio-methanol
yield was maximized during the first week and decreased in
the subsequent weeks. Boiled rice gave the highest biomethanol yield (39.63 wt.%, 2.96 g/mL), followed by grass
(16.78 wt.%, 1.11 g/mL), leaves (16.02 wt.%, 0.92 g/mL), corn
stover (14.80 wt.%, 1.08 g/mL) and banana peels (14.04 wt.%,
0.98 g/mL) in the first week of the digestion experiment.
The accumulated bio-methanol in the reactors from
Experiment 2 was determined at week 6, the final week of the
experiment. The bio-methanol yield in Experiment 2 is presented in Fig. 3. Boiled rice showed the highest bio-methanol
yield (81.25 wt.%, 0.283 g/mL), followed by banana peels
(61.51 wt.%, 0.202 g/mL) and corn husk (1.14 wt.%, 0.004 g/
mL). These results were in line with the results of Experiment; however, leaves and grass failed to produce any biomethanol.
The bio-methanol yield from the anaerobic digestion of
goat dung in Experiment 3 is displayed in Fig. 4. It can be seen
that the bio-methanol concentration in the reactor tend to
increase steadily to a maximum of 0.0024 g/mL on Day 28 and
decreased gradually thereafter. However, the accumulated
bio-methanol percentages were fluctuated throughout the
experiments where the maximum percentage was observed
on day 12 of 73.83 wt.%.
The accumulated bio-methanol in the reactor for Experiment 4 was analyzed at the end of the experiment on day 14
using the analytical high-pressure liquid chromatography
method. Banana peels with goat dung inoculum produced the
highest bio-methanol yield (10.9 wt.% and 0.097 g/mL), followed by boiled rice (2.71 wt.%, 0.024 g/mL); spinach waste
yielded the least bio-methanol (0.35 wt.% and 0.003 g/mL). If
the retention time of the experiment is prolonged, the biomethanol yield is expected to increase.
From Fig. 5, it was observed that banana peels and boiled
rice yielded the highest quantities of bio-methanol as
compared to other waste. The particle size of the rice sample
was small, and as a result, it had a larger surface area on
which the microbial activity could occur. Harun et al. [42]
showed that alkali pre-treatment of lignocellulosic biomass
caused fiber swelling, resulting in an increased internal surface area, a decreased degree of polymerization and level of
cellulose crystallization, a separation of the structural linkages between lignin and carbohydrates (cellulose and hemicellulose) and disturbances to the lignin molecular structure.
These findings explain why the addition of sodium hydroxide
(NaOH) in the reactor promotes increased production of biomethanol during anaerobic digestion.
The anaerobic digestion of bio-solids resulted in high yields
of bio-methanol in all four experiments. The addition of
livestock wastes to agricultural wastes increased the efficiency of the digestion process to produce bio-methanol.
Furthermore, because most of the nitrogen is converted to
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Corn husk
Rice
Banana peels
50
Grass
8
7.5
pH value
7
6.5
6
5.5
5
0
(a)
Corn husk
2
Time (Weeks)
Rice
Banana peels
Grass
pH value
6
5.5
5
4.5
4
3
Time (Weeks)
Grass
20
10
3.5
Boiled rice
Leaf
6.5
Banana peels
30
Time (Weeks)
7.5
Corn stover
40
(b)
Leaf
Leaf
Corn stover
Banana peels
Boiled rice
Grass
3.0
2.5
2.0
1.5
1.0
0.5
0.0
Time (Weeks)
7.4
90
6.8
6.6
6.4
10
(c)
15
20
25
30
35
40
Time (Days)
7.5
Spinach
Sugarcane bagasse
Pineapple peels
Boiled rice
Papaya peels
Banana peels
0.3000
80
Percentage
70
Concentration
0.2500
60
0.2000
50
0.1500
40
0.1000
30
20
0.0500
10
0.0000
0
Corn husk
Leaf
Grass
Banana
peels
Boiled rice
6
5.5
5
4.5
80
0.0030
3.5
3
1
Time (Weeks)
70
0.0025
60
Concentration
Percentage
50
0.0020
40
0.0015
30
0.0010
20
0.0005
10
0.0000
0
4
12
16
20 24 28
Time (Days)
32
36
40
44
pH value
6.5
(d)
pH value
7.2
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0.12
Percent
10
0.1
Concentration
0.08
0.06
0.04
0.02
12
0
Spinach Sugarcane Pineapple Boiled rice Papaya
waste
bagasse
peels
peels
Banana
peels
Anaerobic co-digestion
Type of bio-solids
Cow dung chicken manure
Cow dung
[39]
[40]
[41]
[42]
Anaerobic digestion
Anaerobic co-digestion
Goat dung
Goat dung
Pyrolysis
Deciduous plant
Hazelnut
Tea waste
Olive husk
Peach tree
Agricultural waste
Forestry waste
Animal waste
Corn stover
Leaf
Grass
Banana peels
Boiled rice
Corn stover
Leaf
Grass
Banana peels
Boiled rice
Spinach waste
Sugarcane bagasse
Pineapple peels
Boiled rice
Papaya peels
Banana peels
Maximum bio-methanol
content (wt.%)
14.80
16.02
16.78
14.04
39.63
1.14
e
e
61.51
81.25
73.83
0.35
1.13
0.91
2.77
0.78
10.90
4.11
12.19
10.93
7.65
5.82
0.5e5.93
0.1e4.36
0.4e1.2
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Conclusion
This study shows the potential for the production of biomethanol as intermediate product from bio-solids via anaerobic co-digestion. The digestion of livestock and agricultural
waste resulted in improved bio-methanol yields. The results
of this study suggest that banana peels and boiled rice substrates with cow dung inoculum represent potentially feasible
feedstocks for the production of bio-methanol, as evidenced
by lab-scale experimentation. Cow dung, chicken manure and
goat dung inoculum are very suitable for the digestion of biosolids to produce bio-methanol. Finally it was observed that,
the bio-methanol yield was higher than those of previously
reported studies using pyrolysis technology.
Acknowledgment
The authors are grateful for the financial support provided for
this research under the Research University Grant No UKMGUP-2013-031 and FRGS/2/2013/TK06/UKM/01/1.
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