International Journal of Environment and Bioenergy, 2012, 3(3): 132-144 International Journal of Environment and Bioenergy ISSN: 2165-8951

Florida, USA Journal homepage: www.ModernScientificPress.com/Journals/IJEE.aspx Article

Studies of Biogas Production from Green Seaweeds

Johnner P. Sitompul 1, *, Asep Bayu 1, 2, Tatang H. Soerawidjaja 1, Hyung Woo Lee 1
1

Department of Chemical Engineering, Faculty of Industrial Technology, Institute of Technology Bandung, Jl. Ganesha 10, Bandung, 40132, Indonesia 2 Research Centre for Oceanography, Indonesian Institute of Science (LIPI), Jl. Pasir Putih 1, Ancol Timur, Jakarta, 14430, Indonesia * Author to whom correspondence should be addressed; E-Mail: sitompul@che.itb.ac.id; Tel.: +62-222500989; Fax: +62-22-2501438. Article history: Received 12 June 2012, Received in revised form 7 August 2012, Accepted 8 August 2012, Published 20 August 2012.

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.

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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.

2. Materials and Methods

U. lactuca as the source of biomass was collected from Sayang Heulang Beach (070 40.140S, 1070 41.422E) at Pameungpeuk, West Java, Indonesia on July, 2010. The Biomass was sun dried after cleaned from sands and the dried biomass was then placed in plastic bag and stored at room temperature. Dried biomass was soaked in water for 2 h to get back the initial form of the biomass.
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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

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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.

3. Results and Discussion

3.1. Composition of U. lactuca Table 1 show that U. lactuca from Indonesias coastal area have high water content and less in lignin content with 91.72 and 1.54% (w/w), respectively. The lignin content of U. lactuca is certainly less than that of banana stem waste. Furthermore, total N that resulted was low (1.20%-w) while TOC and C:N ratio of biomass were around 28.29% (w/w) and 23.58% (w/w), respectively. The higher C:N ratio in U. lactuca compared with banana stem waste show that this biomass has good anaeroic biodegradability than banana stem waste. In general, the characteristics show that the U. lactuca from Indonesia has a potency for anaerobic biodegradibillity (AB) process, since substrates with low lignin, high carbohydrate and water content, and moreover C:N ratio ranging from 20:1 to 30:1 will usually have a high of anaerobic biodegradability.

Table 1. Characteristics and composition of U. lactuca and banana stem waste Unit U. lactuca TS* VS Ash Water Lignin TOC Total N C:N
Note: * measured as juice. Copyright 2012 by Modern Scientific Press Company, Florida, USA

Biomass Banana Stem Waste 2.94 86.96 13.04 93.08 7.17 41.38 1.92 21.55 5.65 86.85 13.15 91.72 1.54 28.29 1.20 23.58

%-w %-w %-w %-w %-w %-w %-w

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3.2. Acclimatization of Inoculums Concentration of CH4 as well as CO2 increased smoothly until 14 days which is only cow manure that added in digester as shown in Fig. 2. Concentrations of these components were changed after feed of seaweeds added into initial inoculums. N2 gas was also present dominantly in the biogas and it decreases drastically in the fifteen days of AB process, with the other gases concentration total summed up to 99.6-99.9% for every sampled data. Other traces of components were not identified in the GC. The high productivity of CO2 showed that hydrolysis bacteria as well as acidogenic bacteria can fast adapt with substrate, while methanogenic bacteria still slow since the productivity of CH4 is low. Acclimatization of inoculums is needed since it aims to adapted bacteria with feed environment.

100 80

Concentration (%-v/v)

60 40 20 0 0

CH4

CO2

N2

H2

10

15 Time (days)

20

25

30

Figure 2. Concentrations of each component in the biogas during acclimatization process.

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.
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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.
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Table 2. Process Parameter in anaerobic biodegradation process of U. lactuca Parameter Value Temperature Hydraulic retention time ISR value Digester capacity Volume of digestate Volume of feed Rate of feeding Mesophilic (25-32 oC) 28 days 2:1 5L 3.5 L 5% volume of digestate 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.
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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.

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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.

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Table 3. Typical HHV of common fuels compared with that of the produced biogas from U. lactuca Fuel Wood Soft coal Hard coal Biogas from cow manure Biogas from U. lactuca Biogas from banana stem waste Heating Value (HHV) kJ/g 17 23 35 25.5 15.3 10.8 Btu/lbm 7,700 10,000 15,000 11,000 6,563 This research 4,643
Note: *based on commonly composition of methane and carbon dioxide in biogas with 70% and 30% (v/v), respectively.

References

Felder and Rosseau, 2005

Calculated *

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.
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References
Briand, X., and Morand P. (1997). Anaerobic digestion of Ulva sp. 1. Relationship between Ulva sp. composition and methanisation. J. Appl. Phycol., 9: 511-524. Bruhn, A., Dahl, A., Nielsen, H. B., Nikolaisen, L., Markager, S., Olesen, B., Arias, C., and Jensen, D. (2011). Bioenergy potential of Ulva lactuca, biomass yield, methane production and combustion. Bioresour. Technol., 102: 2595-2604. Bruton, T., Lyons, H., Lerat, Y., Stanley, M., and Rasmussen, M. B. (2009). A Review of the Potential of Marine Algae as a Source of Biofuel in Ireland. Sustainable Energy Ireland Report. Chang, H. N., Kim, N, J., Kang, J., and Jeong, C. M. (2010). Biomass-derived volatile fatty acid platform for fuels and chemicals. Biotechnol. Bioproc. Eng., 15: 1-10. Felder, R. M., and Rousseau, R. W. (2005). Elementary Principles of Chemical Processes. John Wiley and Sons, United States of America, pp. 448-475. Kelly, M. S., and Dworjanyn, S. (2008). The Potential of Marine Biomass for Anaerobic Biogas Production. Marine Estate Research Report, The Crown Estate, Scotland. Kim, S. J., Kim, M. Y., Jeong, S. J., Jang, M. S., and Chung, I. M. (2012). Analysis of the biomass content of various Miscanthus genotypes for biofuel production in Korea. Indus. Crops Prod., 38: 46-49. McKendry, P. (2002). Energy production from biomass (Part 1): Overview of biomass. Bioresour. Technol., 83: 37-46. Migliore, G., Alisi, C., Sprocati, A. R., Massi, E., Ciccoli, R., Lenzi, M., Wang, A., and Cremisini, C. (2012). Anaerobic digestion of macroalgae biomass and sedimnets sourced from the Orbetello Lagoon Italy. Biomass Bioener., 42: 69-77. Murdinah, I., Peranginangin, H. E., Subaryono, R., Sinurat, E., Darmawan, M., and Fransiska, D. (2006). Report (in Indonesian), Riset Teknik Pembuatan Biogas Sebagai Sumber Energi, Laporan Riset, Balai Besar Riset Pengolahan Produk & Bioteknologi Kelautan dan Perikanan, pp. 1-27. Raposo, F., Rubia, M. A. D., Cegri, V. F., and Borja, R. (2011). Anaerobic digestion of solid organic substrates in batch mode: An overview relating to methane yields and experimental procedures. Renew. Sustain. Ener. Rev., 16: 861-877. Sitompul, J., Widayat, P., and Soerawidjaja, T. H. (2012). Evaluation and modification of processes for bioethanol separation and production. Int. J. Renew. Ener. Develop., 1: 15-22. Soerawidjaja, T. H. (2009). Biogas, Lecture Note (in Indonesian): Technology of Chemurgy, Module 13, Institute of Technology Bandung, Bandung, Indonesia, pp. 1-30. World Energy Outlook. (2008). Taken from the website, www.worldenergyoutlook.org.
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Yudhistira (2009). Pemanfaatan Rumput Laut Sebagai Bahan Baku Produksi Gas Metana. Thesis (in Indonesian), University of Diponegoro, Semarang, Indonesia. Zeng, S. Y., Shi, X., and Qiu, Y. (2010). Effect of inoculum/substrate ratio on methane yield and orthophosphate release from anaerobic digestion of Microcystis sp., J. Hazard. Mater., 178: 89-93.

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