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Determination of bio-methanol as intermediate


product of anaerobic co-digestion in animal and
agriculture wastes
M. Anitha a, S.K. Kamarudin a,b,*, N.S. Shamsul b, N.T. Kofli a
a

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

article info

abstract

Article history:

Many researchers have reported on the end products of the anaerobic digestion process as

Received 9 September 2014

biogas and methane but the useful intermediate products in the anaerobic digester

Received in revised form

effluent, such as bio-methanol have typically been ignored. Bio-methanol is an auspicious

10 June 2015

substitute for fossil fuels with a variety of fuel applications and advantages with regard to

Accepted 12 June 2015

the environment, the economy, and consumers. Thus the main objective of this study is to

Available online 10 July 2015

investigate the intermediate product of anaerobic co-digestion of animal and agriculture


wastes. The wastes are characterized based on proximate and ultimate analyses. This

Keywords:

study was conducted in a room temperature, lab-scale reactor with a fixed retention time.

Methanol

Methanol was analyzed using high-pressure liquid chromatography (HPLC). It was

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

search for alternative energy sources. Renewable energy is


expected to become an important source of energy and will
contribute 18% of the global energy supply by 2030 [3].
Switching from fossil fuels to renewable energy brings positive impacts such as reduced emissions of toxic and greenhouse gases, a greener environment and healthier
community, as well as the promise of a sustainable future.
Although renewable technology currently incurs high development and management costs for large-scale energy and

* 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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renewable material production, further research to develop


cheap, clean and eco-friendly products is underway.
Methanol has attracted attention as an alternative transport fuel when blended in various proportions and is currently
under consideration for wider use [4]. Methanol that falls into
the liquid biofuel category is currently under development by
researchers. The steadily increasing prices of crude oil and
petroleum have increased the viability of commercial-scale
biofuel production. Methanol is a major feedstock in the
petrochemical industry and has recently been considered as
an emerging renewable liquid transportation fuel and a
replacement for non-renewable fossil fuels. Alcohol fuels
from methanol have been well known in the racing community for years because of their safety and performance advantages compared to gasoline as well as their higher octane
number, which offers a slight edge in power compared to
ethanol [5]. Agarwal et al. [6] studied on methanol-gasoline
blended fuel in a medium duty spark ignition transportation
engine and it was found that the gasohol emitted lower CO,
NO and smoke than gasoline, combustion characteristic of
gasohol blends are similar to gasoline and suggested that the
methanol can be excellent substitute for gasoline for transportation engines without any hardware amendment. Besides
that, methanol can also be used as a source of energy for direct
methanol fuel cell, a type of proton exchange membrane fuel
cells (PEMFCs) which can be used for portable electronics and
vehicle applications due its benefits of cheap, small, ecofriendly and able to replace conventional batteries in the
future [7,8]. Based on from the research conducted by Rashidi
et al. [9], it is remarkable to found that DMFC system is lowcost, occupies less space than Li-ion battery to store energy
and higher exegetic efficiency of DMFC causes less emissions
of carbon dioxide.
The majority of the methanol produced for commercial
applications is synthesized through the pyrolysis conversion
pathway to synthesis gas (syngas). However, the feedstocks
may vary. Pyrolysis is a thermal decomposition process in
which organic matter in the biomass is converted into bio-oil
(methanol) in the absence of oxygen or in an atmosphere
containing significantly less oxygen than is required for
complete combustion [10,11]. These processes are characterized by high energy consumption, low conversion efficiency
rates, and high capital costs [12]. However, bio-methanol can
be produced via a cheaper process that consumes less energy
and space by anaerobic digestion.
Many researchers have conducted research on the yield of
valuable products and by-products that can be extracted or
produced through the anaerobic digestion of biomass, solid
waste, or sewage. Wang & Blaschek [13] studied the fermentation of mixed sugar from tropical maize stalk juice with
Clostridium beijerinckii NCIMB 8052 to produce butanol. Zhu
et al. [14] studied anaerobic co-digestion of municipal food
waste and sewage sludge for the production of biohydrogen.
Sharma et al. [15] were successful in the increased production
of biogas and methane by anaerobic co-digestion of poultry
litter and thin stillage in a pilot-scale thermophilic continuous
stirred tank reactor (CSTR). Liu et al. [16] conducted a research
study on the anaerobic co-digestion of municipal biomass
waste and dewatered sewage sludge and achieved a stable
operation with high biogas production. Anaerobic mesophilic

co-digestion of pig manure and glycerin was studied by Astals


et al. [17], who found that, interestingly, co-digestion
increased methane production. Rivero et al. [18] investigated
on anaerobic co-digestion of mixed sewage sludge and crude
glycerol from biodiesel industry at mesophilic condition in a
laboratory scaled semi-continuous CSTR, found that high
removal of volatile solids, the hydrogen and methane yield
enhanced significantly. Although many researchers have reported on the manufacture of end products of the anaerobic
digestion process, particularly biogas and methane [19e21],
the useful intermediate products in the anaerobic digester
effluent, such as bio-methanol, have typically been ignored.
Bio-methanol is an auspicious substitute for fossil fuels with a
variety of fuel applications and advantages with regard to the
environment, the economy, and consumers.
Thus, this work is an exploratory study of bio-methanol as
intermediate product via anaerobic digestion. In this work,
anaerobic digestion of different types of bio-solids was
investigated using laboratory-scale reactors. The main objective of this study was to determine the bio-methanol yields for
the solid-state digestion of different livestock and agricultural
wastes via anaerobic digestion.
The anaerobic digestion of bio-solids involves biological
conversion of soluble, dissolved organic matter into biogas
(methane and carbon dioxide), alcohols (bio-methanol and
other higher molecular weight alcohols), volatile fatty acids
and nitrogen-rich organic residues. Anaerobic digestion offers
many benefits, including low levels of biological sludge, high
efficiency, and low nutrient requirements [22]. It is also an
attractive waste treatment practice to control pollution and
recover energy [23]. It is experimentally proven herein that the
performance and yield of a digestion process can be improved
when different wastes are mixed and digested together. This
process is termed as anaerobic co-digestion. Anaerobic codigestion is a waste treatment method in which different
wastes are mixed and treated together [24]. Co-digestion has
been used to increase the yield of anaerobic digestion of
organic waste. Cuetos et al. [25] have observed that codigestion stabilizes the bio-solid mixture in the bioreactor,
increases the C/N ratio and reduces the nitrogen concentration. Khalid et al. [26] stated that the utilization of cosubstrates with low nitrogen content promotes the production of biogas because the different features of each type of
waste are complimentary, thus reducing the problems associated with single-substrate anaerobic digestion, including
the accumulation of volatile compounds and high ammonia
concentrations. The recent research conducted by Miao et al.
(2014) [27] to evaluate methane production by co-digestion at
different inoculum to substrate ratios (ISRs) of Taihu blue
algae and swine manure. The results indicated that codigestion of blue algae and swine manure at produced high
methane yield than the digestion of blue algae inoculated with
granular sludge.
Besides, poorly managed and untreated animal manure
can become a major cause of water and air pollution. Livestock sector releases about 14.5% of total global greenhouse
emissions, which is more than direct emissions from the
transport sector [28]. Manure can be a beneficial resource for
the production of renewable energy and as a source of
nutrient-rich agricultural fertilizer [29]. Glucose and other

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fermentable monosaccharide can be converted from readily


available cattle manure, which is a lignocellulosic biomass
[30]. From the experiment conducted by Teater et al. [30], it
was found that hemicelluloses were consumed at a much
faster rate than cellulose in the anaerobic digestion process.
This rapid breakdown of hemicelluloses facilitated the
breakdown of the matrix structure of the manure fiber. As a
result, the solid effluent of anaerobic digestion was more
easily enzymatically hydrolyzed than raw manure fiber. Yue
et al. [31] found that the anaerobic digestion of manure fiber
produced a quality similar to that of other cellulosic feedstocks. Hence, it is believed that the yield of bio-methanol via
the anaerobic digestion process can be increased by mixing
the lignocellulosic substrates.

Table 1 e Types of bio-solids.


Type of bio-solid
Livestock waste
Cow dung
Chicken manure
Goat dung
Agricultural waste
Corn stover
Banana peels
Grass
Fallen leaves
Boiled rice

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.

Anaerobic digestion of bio-solids


The prepared mixture of bio-solids described in Section 2.1
was introduced into each reactor. Nitrogen (N2) gas was
sparged into the reactor for 10 min before beginning the
experiment to ensure anaerobic conditions in the reactor. The
digestion experiment was carried out at psychrophilic temperature (25  C) conditions. The reactor was manually agitated
daily to homogenize the suspended solids in the reactor. The
pH value of each reactor was determined weekly. A 2 M NaOH
solution was used to regulate the pH of the reactor within a
range of 6.5e7.5. All the procedures were carried out under
anaerobic (nitrogen-rich) atmospheric conditions to avoid the
introduction of oxygen to the reactor system. To determine
the practicality of the anaerobic digestion of bio-solids, four
semi-continuous experiments were conducted. Table 2 shows
the experimental conditions of the digestion processes for the
semi-continuous experiments.

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

To analyze the liquid product, the reactor content was


mixed until completely miscible. The samples were then
centrifuged at 8000 rpm for 5 min to separate the solid and
liquid layers. The supernatant was removed carefully using a
disposable syringe with a 0.45 mm centrifuge filter to analyze
the methanol composition using the analytical high-pressure
liquid chromatography (HPLC) method.

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.

Results and discussion


Proximate analysis
Table 3 shows the results of the proximate analysis of the biosolids. Boiled rice (48.84 wt.%) had the lowest total solid content among the livestock and other agricultural wastes,
whereas fallen leaves had the highest total solids content at
92.56 wt.%. The volatile matter was lowest in sugarcane
bagasse (0.05 wt.%) and highest in fallen leaves (93.57 wt.%).

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Table 2 e Summary of reactor conditions.


Experiment

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

Accumulation in reactor for 6 weeks

4 days interval
Accumulation in reactor for 2 weeks

50% Cow dung 50% chicken manure 10%


50% Cow dung 50% chicken manure 10%
50% Cow dung 50% chicken manure 10%
50% Cow dung 50% chicken manure 10%
50% Cow dung 50% chicken manure 10%
50% Cow dung 50% corn stover
100% Cow dung 10% banana peel
100% Cow dung 10% boiled rice
100% Cow dung 10% grass
100% Cow dung 10% leaf
100% Goat dung
50% Goat dung 50% boiled rice
50% Goat dung 50% sugarcane bagasse
50% Goat dung 50% pineapple peels
50% Goat dung 50% spinach waste
50% Goat dung 50% papaya peels
50% Goat dung 50% banana peels

corn stover
banana peel
boiled rice
grass
leaf

Table 3 e Proximate analysis of bio-solid samples.


Samples
Livestock waste
Cow dung
Chicken manure
Goat dung
Agricultural waste
Boiled rice
Pineapple peels
Spinach waste
Sugarcane bagasse
Banana peels
Papaya peels
Corn stover
Grass
Fallen leaves

Total solid (wt.%)

Volatile matter (wt.%)

Moisture content (wt.%)

Ash (wt.%)

Fixed carbon (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.

The highest moisture content was observed in grass


(66.13 wt.%), and the lowest was observed in fallen leaves
(7.44 wt.%). Fallen leaves exhibited the highest ash content at
15.57 wt.%, while the lowest was observed in boiled rice
(1.71 wt.%). Grass showed the lowest percentage of fixed carbon (2.94 wt.%), whereas sugarcane bagasse had the highest
value (63.88 wt.%).

showed the highest C/N ratio (15.39), followed by chicken


manure (14.43) and cow dung (6.18). Conversely, agricultural
wastes showed comparatively lower C/N ratios than livestock
wastes. Spinach waste exhibited the lowest C/N ratio (1.14)
among the agricultural wastes. Boiled rice had the highest C/N
ratio (8.09). Thus, adding livestock wastes to agricultural
wastes improves the C/N ratio and provides nutrients for
microbial reactions during the digestion process.

Elemental composition analysis


Table 4 presents the carbon, hydrogen, nitrogen and oxygen
contents of the bio-solids. Relatively higher carbon contents
were observed in livestock wastesdcow dung (25.62%),
chicken manure (21.93%) and goat dung (36.16%)dand in
boiled rice (20.79%) than in other wastes. Spinach waste had
the lowest carbon content at 2.94%.

Carbon to nitrogen (C/N) ratio


From Table 4, the C/N ratios of the livestock wastes were
higher than those of other agricultural wastes. Goat dung

pH variation during anaerobic digestion


At the beginning of the experiment, the pH values of the reactors were in the range of 6.9e7.1. Fig. 1 shows pH changes in
the reactors during anaerobic co-digestion for each reaction
mixture. The pH of the reaction mixture fell rapidly in each
reactor because the more biodegradable organic fraction had
been hydrolyzed and converted into volatile fatty acids (VFAs).
A 2 M NaOH solution was added to each reactor as appropriate
to regulate the pH of the reactors and avoid methanogenesis
inhibition at low pH. From previous studies, it was observed
that a pH range of 6.5e7.5 was favorable for methanogenesis

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Table 4 e Elemental composition analysis.


Samples
Cow dung chicken manure
Cow dung chicken manure
Cow dung chicken manure
Cow dung chicken manure
Cow dung chicken manure
Cow dung corn stover
Cow dung banana peel
Cow dung grass
Cow dung boiled rice
Cow dung leaves
Cow dung
Goat dung
Chicken manure
Boiled rice
Pineapple peels
Spinach waste
Sugarcane bagasse
Banana peels
Papaya peels

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

and bio-methanol yield. This result is in agreement with the


rnsson
studies of Ward et al. [37] and Lee et al. [38]. Nges & Bjo
[39] stated that pH values above 6.8 were considered indicative
of stable processes and, hence, active methanogenesis. VFAs,
the intermediates during methanogenesis, play a significant
controlling role in the anaerobic digestion process. VFAs are
utilized by the acetogenic and methanogenic microbial populations as soon as they appear in the medium, and hence,
VFAs are found only at low concentrations in well-balanced
digesters [40]. The accumulation of VFAs in the reactor early
in the anaerobic digestion experiment lowered the pH of the
reactor mixture in all four experiments. However, the pH
values started to gradually increase when VFAs were converted through methanogenesis as they were consumed by
the methanogen. Fluctuations in the reactor pH were likely
due to the periodic accumulation, conversion, and consumption of VFAs in methanogenesis [41].

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

Bio-methanol content (vol.%)

8
7.5
pH value

7
6.5
6
5.5
5
0

(a)

Corn husk

2
Time (Weeks)

Rice

Banana peels

Grass

Bio-methanol concentration (g/mL)

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)

Fig. 2 e Bio-methanol yields for Experiment 1.

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

Fig. 3 e Bio-methanol yields for Experiment 2.

6
5.5
5
4.5

80

0.0030

3.5
3
1

Time (Weeks)

Fig. 1 e pH of reactor (a) Experiment 1 (b) Experiment 2 (c)


Experiment 3 (d) Experiment 4.

ammonia nitrogen in anaerobic digestion, which is toxic to


microbial metabolism [43], using poultry waste as a substrate
in anaerobic digestion could increase the risk of process inhibition [44]. It is observed (Table 4) that the nitrogen content
in chicken manure is higher than in cow dung. Hence, the bio-

Bio-methanol percentage (%)

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

Fig. 4 e Bio-methanol yields for Experiment 3.

Bio-methanol concentration (g/mL)

pH value

6.5

(d)

Bio-methanol concentration (g/mL)

Bio-methanol content (wt. %)

pH value

7.2

11797

i n t e r n a t i o n a l j o u r n a l o f h y d r o g e n e n e r g y 4 0 ( 2 0 1 5 ) 1 1 7 9 1 e1 1 7 9 9

0.12
Percent

10

0.1

Concentration

0.08

0.06

0.04

0.02

Bio-methanol concentrattion (g/mL)

Bio-methanol content (wt. %)

12

0
Spinach Sugarcane Pineapple Boiled rice Papaya
waste
bagasse
peels
peels

Banana
peels

Fig. 5 e Bio-methanol yields for Experiment 4.

methanol yield using cow dung inoculum was higher than


those obtained using mixtures of cow dung and chicken
manure inoculum.
The hydraulic retention time of an anaerobic digestion
process to produce bio-methanol is an important factor in
controlling the yield of bio-methanol. This is because biomethanol is an intermediate product in the digestion process. As stated by Chandra et al. [45], in the acidogenesis
phase, monomers produced from hydrolysis degrade to shortchain organic acids, molecules C1 e C5 (i.e., butyric acid, propionic acid, acetate and acetic acid), alcohols, hydrogen and
carbon dioxide. This results in increased bio-methanol production in the beginning of the experiments. The decline in
the production of bio-methanol can be explained by the conversion of bio-methanol to acetate and methane in the acetogenesis and methanogenesis processes, respectively.

Table 5 shows the comparison of bio-methanol in the


liquid effluent of digestion with the results of previous
studies. This seems to be the first report of bio-methanol
production via anaerobic digestion. Thus, the production of
bio-methanol was compared with the pyrolysis of biomass for
syngas production and subsequent bio-methanol synthesis
through catalysis. The bio-methanol yield using anaerobic
digestion was considerably higher than that of the pyrolysis
method.
The anaerobic digestion process of cow dung, chicken
manure and goat dung with agricultural wastes favors biomethanol production. In Experiment 1 (cow dung chicken
manure boiled rice), the digested sample produced
39.63 wt.% bio-methanol. Significantly higher bio-methanol
percentages were produced in Experiment 2 (cow
dung boiled rice, 81.25 wt.%; cow dung banana peels,
61.51 wt.%). Experiment 3 (goat dung) produced 73.83 wt.%
bio-methanol, while (goat dung banana peels) produced
10.90 wt.% bio-methanol. Demirbas [46e48] reported the production of bio-methanol (pyro-oil) from bio-solids using the
pyrolysis conversion method. The pyrolysis of hazelnut and
tea waste produced, respectively, 12.19 wt.% and 10.93 wt.%
bio-methanol; these yields are lower than those produced by
the digestion process reported herein. Kamarudin et al. [49]
reported 0.5e5.93 wt.%, 0.1e4.36 wt.%, and 0.4e1.2 wt.% biomethanol yields produced from agricultural, forestry, and
animal wastes, respectively, via pyrolysis. Additionally, the
bio-methanol yield produced from anaerobic digestion was
higher than that obtained using pyrolysis technology.
Further research is required to explain how the composition and structure of lignocellulose material affect the yield of
bio-methanol from anaerobic digestion. Detailed studies of

Table 5 e Comparison of bio-methanol yield.


Biomass conversion technology
This study

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

11798

i n t e r n a t i o n a l j o u r n a l o f h y d r o g e n e n e r g y 4 0 ( 2 0 1 5 ) 1 1 7 9 1 e1 1 7 9 9

the controlling factors, such as the operational temperature,


the particle size of the digested bio-solids, the VFAs produced,
and factors affecting ammonia nitrogen accumulation, should
be performed to more fully understand the bio-methanol
yield.

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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