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Abstract: Marine biomasses such as green seaweeds are reported to contain far less lignin
than terrestrial biomass and thus conceptually making them good feedstock for biogas
production. The objective of this research is to investigate the potential of green seaweed
Ulva lactuca from Indonesia as a feedstock for biogas production. A semi-pilot scale
experiment with 5-L digester was set up to study the potential of the green seaweed as
feedstock to produce biogas. Wet biomass was mixed and blended with water in 1:2 ratios
to produce feedstock juice. The juice was then mixed with inoculums prepared from earlier
processes and 3.5 L of this mixture was added to a 5 L-bioreactor or digester. The initial
inoculums were prepared from cow manure and water. The semi-continuous process was
applied for the anaerobic biodegradation of slurry in the digester. The biogas generated was
measured daily to study the biodegradability of the biomass and further, chemically oxygen
demand (COD) of the slurry was measured. The flammability test was also conducted to
check the combustibility of the produced biogas. The methane and carbon dioxide contents
of the generated biogas were around 49.90% and 43.93%, respectively. The gas was
flammable and has calculated high heating value (HHV) 15.3 kJ/g-biogas, based on
methane content. This research has thus shown that green seaweeds are quite promising
feedstock for biogas production in coastal areas.
Keywords: seaweeds; macroalgae; Ulva lactuca, banana stem waste; anaerobic
biodegradability; biogas production; high heating value.
133
1. Introduction
The crisis in the world during 1970s decade has driven industries to use energy more
efficiently. Furthermore, the world energy demand has increased significantly during the new
millennium and is predicted to be 700 quadrillion BTU in 2030 from 400 quadrillion in 2000 (World
Energy Outlook, 2008). Hence, most of current research with regard to energy has been focusing in
finding invention of new energy and renewable energy as well as efficient utilization of energy in
many processes (Sitompul et al., 2012).
Biomass conversion to energy is a very crucial step for producing renewable energy from
biomass. Marine biomasses such as seaweeds, also known as macroalgae, were reported to be biomass
resources for biogas because they have good anaerobic biodegradability for biogas production. This is
due to seaweeds not only have high of carbohydrate (25-60%-w) and water content (70-90%-w), but
also low of lignin content (1-7%-w) as reported by Bruton et al. 2009, Bruhn et al. 2010, Chang et al.
2010, among others. Green seaweeds as well as brown seaweeds were reported as a good candidate of
feedstock for producing biogas because of high methane yields (Bruhn et al., 2010; Bruton et al., 2009;
Kelly and Dworjanyn, 2008).
Indonesia has a large number of marine biodiversity including seaweeds. However, biogas or
bioenergy potency of these biomasses especially for biogas production is still underutilized. Seaweeds,
such as Eucheuma sp., Gracillaria sp., and Sargassum sp. (Murdinah et al., 2006; Yudhistira, 2009),
has been an economic value and can used as feedstock to produce biogas. Ulva lactuca is one of green
seaweeds found in many coastal areas of Indonesia. It has high potential growth rates than terrestrial
plants (McKendry, 2002), moreover high level of accessible sugars (Bruton et al., 2009; Kelly and
Dworjanyn, 2008). This biomass was considered as one of a potential aquatic energy crops (Bruhn et
al., 2010). However, the anaerobic biodegradability of this biomass which grows in coastal areas of
Indonesia has not been reported. In this study, the potency of U. lactuca from Indonesia for producing
biogas is studied in a mini-pilot scale digester as well as the combustibility and the gross or high
heating value (HHV) of the produced biogas. Further, a terrestrial biomass, banana stem waste, was
used as comparison.
134
Wet biomass was cut into small pieces and mixed and blended with water in 1:2 ratios to produce juice
as a feed of substrate. The experimental set up is shown in Fig. 1. A mini-pilot digester experimental
set up was consisted of a 5 L plastic bottle as a main digester (D), gas collecting tank (GT) and water
collecting tank (WT). Biodegradation process will occur in D while biogas which is produced from
process will be collected in GT. Volume of biogas was measured from the change of water level on
GT, while methane and carbon dioxide content in biogas were measured with gas chromatograph
(Shimadzu GC-8A with Porapak Q and Molecular Sieve 5A). The sampling of the biogas was taken by
a syringe through a sampling port before GT.
Figure 1. Experimental set-up for biogas production from green seaweeds. Note: (1) inlet port, (2)
main digester (D), (3) gas collecting tank (GT), (4) water collecting tank (WT), (5) sampling port, (6)
drain port.
The experiments started with acclimatization process by preparing inoculums. The inoculums
were prepared from mixture of cow manure and water in a 1:1 ratio. About 3.5 L of this mixture were
then placed into digester and fermented about 14 days. Furthermore, 5% (v/v) of feed was added daily
and at the same time, slurry also was removed with the same volume. This procedure was conducted
until 30 days and the volume of biogas as well as composition of biogas was measured daily.
After preparation of the inoculums, anaerobic biodegradation (AB) process was conducted. The
inoculums that resulted from earlier process were then mixed with substrate/biomass in 1:1 ratio, and it
was added to the 5-L digester. Furthermore, 175 mL feed was added every 3 days and slurry also was
removed at the same time. AB process was conducted until 28 days. Volume and composition of
biogas were measured daily. A terrestrial biomass, banana stem waste, was used as comparison since it
also has high of water and carbohydrate content as well as available abundantly in Indonesia. AB
135
process also was conducted with 2:1 of inoculums substrate ratio (ISR) to know the effect of ISR.
Flammability test of the produced biogas was also conducted with Bunsen burner, while higher heating
value (HHV) was calculated based on composition of the biogas (Felder and Rousseau, 2005).
The Analytical methods for measuring total solids (TS), volatile solids (VS), water and ash
content in biomass were determined according to Briand and Morrand (1997) procedure. Lignin was
assayed with Klasson method according to Kim et al. (2012). Chemical oxygen demand (COD) was
analysed using K2Cr2O7 via titration method while total organic carbon (TOC) using Walkley and
Black method. Further, total nitrogen (N) was analysed using Kjeldahl method. Methane and carbon
dioxide contents in the produced biogas were measured with gas chromatography.
Biomass
U. lactuca
TS*
%-w
5.65
2.94
VS
%-w
86.85
86.96
Ash
%-w
13.15
13.04
Water
%-w
91.72
93.08
Lignin
%-w
1.54
7.17
TOC
%-w
28.29
41.38
Total N
%-w
1.20
1.92
23.58
21.55
C:N
Note: * measured as juice.
136
100
Concentration (%-v/v)
80
60
CH4
CO2
N2
10
15
H2
40
20
0
0
20
25
30
Time (days)
Acclimatization can influence the activity of methanogenic bacteria toward a wide variety of
potentially inhibitory substance. Kelly and Dworjanyn (2008) noted that inoculums which were not
acclimating can be direct use for substrate of marine seaweeds but the AB process performs slow
process. However, this results show that inoculums from cow manure were needed for acclimatization
and can adapt with substrate of U. lactuca.
3.3. Effect of ISR
The amount of ISR can affect the productivity of biogas as shown in Fig. 3. ISR 2:1 giving
high biogas production than ISR 1:1 with 2.7 L and 1.4 L, respectively. The high of inoculums in ISR
is needed because it can increase the AB processes. Further, the higher content of bacteria than
substrate, the faster biodegradation will occur.
Copyright 2012 by Modern Scientific Press Company, Florida, USA
137
Figure 3. Effect of ISR toward cumulative volume of biogas. Feed was added daily about 175 mL to
3.5 L of digestate and the same time slurry was exited with the same volume.
Fig. 4 also shows that the amount of ISR can affect the concentrations of each component gas
in biogas. The higher ISR will increase the yields of methane in biogas while carbon dioxide gas
decreasing. Furthermore, yield of hydrogen seems not influenced by the ISR. These results show that
methane production rate will increase with increasing of ISR because of high methanogenic bacteria in
ISR 2:1, compared with ISR 1:1. However, Raposo et al. (2011) noted that theoretically ISR should be
independent toward methane yield and only affect the kinetic of the process. As stated above, other
gas, N2 gas, was also present in the biogas and with the other gases summed up to 99.6-99.9% for
every sampled data.
Rate of substrate feeding also was observed and it can affect the methane production in biogas.
The experimental results show that high methane productivity was occurred when feed was added
every 3 days and low methane productivity when feed was added daily. Therefore, AB process of U.
lactuca was continued with ISR 2:1 and with the rate of substrate feeding every 3 days.
3.4. Comparison of AB Process and Biogas Production from U. lactuca and Banana Stem Waste
Anaerobic biodegradation of U. lactuca was conducted with condition as shown in Table 2.
Biogas produced in the end of process (28 days) is higher than that produced from banana stem waste
with 4.88 L and 3.06 L, respectively. Furthermore, productivity of methane from biogas U. lactuca is
also higher than banana stem waste (see Fig. 5).
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(a)
(b)
(c)
Figure 4. Effect of ISR towards productivity of methane (a), carbon dioxide (b) and hydrogen (c) in
biogas from U. lactuca. Feed was added daily about 175 mL to 3.5 L of digestate and in same time
slurry was exited with the same volume.
Copyright 2012 by Modern Scientific Press Company, Florida, USA
139
28 days
ISR value
2:1
Digester capacity
5L
Volume of digestate
3.5 L
Volume of feed
5% volume of digestate
Rate of feeding
Every 3 days
Figure 5. Methane, carbon dioxide and hydrogen content in biogas from U. lactuca (a) and banana
stem waste (b). The process parameters are given in the Table 2.
Copyright 2012 by Modern Scientific Press Company, Florida, USA
140
The results show that anaerobic biodegradability of U. lactuca is higher than that of terrestrial
biomass since it has low of lignin. Some authors also reported that methane yield of biogas from Ulva
sp. commonly is around 49-60% (v/v) (Briand and Morand, 1997; Migliore et al., 2012). However,
these results can vary depend on time and pretreatment of the biomass.
In general, content of methane in biogas, especially from cow manure, is similar with that of
carbon dioxide (Soerawidjaja, 2009) due to reaction balance from hydrocarbon feedstock. Fig. 5 shows
that methane and carbon dioxide ratio in biogas of U. lactuca is almost the same. This result indicates
that the activity of methanogenic bacteria is quite slow. It may be caused by the high of sulfur content
in U. lactuca that reported by Briand and Morrand (1997) commonly around 2.8-4.4%-w.
The high sulfur can affect activity of methanogenic bacteria since it can also be activated by
sulfuric reducing bacteria (SRB) as reported by Migliore et al. (2012). Although sulfur content in
biomass as well as H2S content in biogas was not quantified from the gas chromatograph data, the
smell of H2S gas was occurred during flammability test of the biogas. SRB was unwanted because it
can affect the competitiveness between methanogenesis and sulphate reducing processes as reported by
Migliore et al. (2012). The higher methane in biogas also might be the indication of fat or triglycerides
presence in the biomass.
The AB process for each feedstock was also studied by measuring chemical oxygen demand
(COD) of the slurry in the digester and all of data are sampled triplicate. Fig. 6 shows the profile of
COD decrease of the slurry in the bioreactor for different biomasses. The results supports the higher
biodegradability of microalgae with COD value during bioprocessing decreasing to the COD value
around 48.6% and 10.2% of its initial value for Ulva lactuca and banana stem waste, respectively. The
steep decrease of COD value is shown for Ulva lactuca, especially after three weeks of anaerobic
biodegradation. The results further supported that the anaerobic biodegradability of macroalgae are
much faster for marine biomass due to far less lignin than terrestrial biomass.
3.5. Flammability Test and Heating Value
Fig. 7 showed the flammability test for the biogas of U. lactuca as well as that of banana stem
waste. They were combustible and gave a blue fire with gross or high heating value (HHV) 15.3 kJ/g.
The HHV is still lower compared with that of biogas from cow manure and that of other solid fuels but
that of U. lactuca is much higher than that of banana stem waste, 10.8 kJ/g, as shown in Table 3.
Furthermore, this value will increase when methane content in the biogas increasing. Therefore, further
research, especially finding the optimum operating condition as well as its parameters, is needed to
increase the methane content in biogas from U. lactuca.
141
Figure 6. The profile of decreasing COD during AB Process for different biomasses.
Figure 7. Flammability test of biogas produced from biomass U. lactuca (a) and that from banana
stem waste (b).
In general, the above results of biogas production from semi-pilot scale digester show that
green seaweeds U. lactuca from the coastal areas of Indonesia were highly potential to produce biogas
production. With the promising results, further research and development works, especially to find
optimum operating condition of the mini-pilot digester is needed.
142
Table 3. Typical HHV of common fuels compared with that of the produced biogas from U. lactuca
Heating Value (HHV)
Fuel
kJ/g
Btu/lbm
Wood
17
7,700
Soft coal
23
10,000
Hard coal
35
15,000
25.5
11,000
15.3
6,563
References
Calculated *
This research
10.8
4,643
Note: *based on commonly composition of methane and carbon dioxide in biogas with 70% and 30% (v/v), respectively.
4. Conclusions
Green seaweeds, especially U. lactuca, are potential renewable resources for producing biogas
due to their better anaerobic biodegradability than terrestrial biomasses such as banana stem waste.
The mini-pilot scale experiment shows that the volume of biogas from the green seaweed feedstock is
about 4.88 L (measured at standard P and T), with methane content of the generated biogas 49.90%
(v/v). The volume and methane contents of produced biogas are higher than that produced from banana
stem waste with 3.06 L biogas and 28.85% of methane, respectively. The HHV of the biogas from U.
lactuca, 15.3 kJ/g, is much higher than that of banana stem waste, 10.8 kJ/g, however, it is still lower
than that of biogas from cow manure, 25.5 kJ/g. Considering the abundant biomass of U. lactuca in
coastal areas of Indonesia, this will make U. lactuca as potential and promising biomass to produce
biogas and become an alternative energy in the coastal area of Indonesia. Therefore, further research to
find optimum operating condition of the mini-pilot digester is needed in order to put this potential into
reality.
Acknowledgement
We would like to thank Mr. Komari at the Department of Chemical Engineering ITB for his
assistance with gas chromatography and to Marine Natural Product Laboratory, Research Centre for
Oceanography LIPI, for characterizing of biomass. Dr. Lee is currently a visiting scholar from
National Research of Foundation, Korea, assigned at the Department of Chemical Engineering, Faculty
of Industrial Technology, Institute of Technology Bandung, Indonesia.
Copyright 2012 by Modern Scientific Press Company, Florida, USA
143
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