Fuel Processing Technology 86 (2005) 1679 1693 www.elsevier.

com/locate/fuproc

Utilization of macro-algae for enhanced CO2 fixation and biofuels production: Development of a computing software for an LCA study
Michele ArestaT, Angela Dibenedetto, Grazia Barberio
IAMC, Department of Chemistry and CIRCC, University of Bari, Campus Universitario, 70126 Bari, Italy

Abstract A Life Cycle Assessment study was carried out for evaluating the potential of utilizing marine biomass for energy production. Macro-algae obtained from the Adriatic and Jonian seas have been selected and tested for our initial case. Different techniques (supercritical CO2, organic solvents, and pyrolysis) were utilized in this study for the extraction of biofuel. Supercritical CO2 appears to be the most effective. A computing software has been developed which allows to evaluate various options and can be used with either aquatic or terrestrial biomass. It has been used in our studies to make an energetic evaluation of selected marine macro-algae. The results of the energetic assessment are presented here. D 2005 Elsevier B.V. All rights reserved.
Keywords: Macro-algae; CO2 fixation; Fuel production; Life cycle assessment (LCA)

Abbreviations: LCA, life cycle assessment; LCI, life cycle inventory; scCO2, supercritical carbon dioxide; MEA, monoethanolamine, HOCH2CH2NH2; SETAC, Society of Environmental Toxicology and Chemistry; SCFE, supercritical fluid extraction; Enet, net energy; Eric, energy recovered as heat from the flue gases; Eb, energy associated to the extracted biofuel; Ers, energy of the residual solid after extraction; Ets, transport energy; Esa, separation energy using MEA; Escr, separation energy using cryogeny; Ed, energy of distribution of CO2; EdV, energy for the distribution of the flue gas; Ec, energy for algae cultivation; Enu, energy associated with supplied nutrients; Eh, energy for algae harvesting; Edr, energy for algae drying; Epr, energy for algae pretreatment; Esc, energy for extraction with scCO2; Eso, energy for extraction with organic solvents; Ees, energy for processing biofuel. * Corresponding author. Tel.: +39 80 544 20 84; fax: +39 80 544 20 83. E-mail address: m.aresta@chimica.uniba.it (M. Aresta). 0378-3820/$ - see front matter D 2005 Elsevier B.V. All rights reserved. doi:10.1016/j.fuproc.2005.01.016

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1. Introduction Biomass, either terrestrial or aquatic, is considered a renewable energy source with quasi zero-emission. Among alternative energy sources, biomass represents the most ready to be implemented on a large scale without any environmental or economic penalty. The photosynthetic efficiency of aquatic biomass results to be much higher (6 8%, average) than that of terrestrial (1.82.2%, average). This makes the former more adapt for an enhanced CO2 fixation to afford a high biomass production. Also, aquatic biomass presents an easy adaptability to grow in different conditions, either in fresh- or marine-waters, and in a wide enough range of pH [1]. The pond culture of algae presents the advantage of assimilating carbon dioxide emitted by electric power plants [2b,c,3,4], using wastewater that may supply the amount of required nutrients [5]. Either marine micro-algae or seaweed could be used for solar energy conversion and biofuel production. Micro-algae have received so far more attention [6,7] with respect to macro-algae [8,9] as agents for enhanced CO2 fixation due to their facile adaptability to grow in ponds or bioreactors and the extended knowledge on several strains used for fish feeding. Macro-algae are extensively grown and used as food in Asiatic Countries, or as source of chemicals. They are usually collected from natural water basins where they are seasonally available. Only recently they have been considered for energy production, and the potential of some Pacific Ocean strains has been preliminarily studied [8]. As extension of our studies on CO2 chemical utilization [2a], we have started a Research Programme aimed at evaluating the potential of selected Mediterranean macroalgae for biofuel production integrating the capture of CO2 from continuous point sources (power plants, industries), its purification, distribution with uptake by macro-algae and their processing. The Programme includes the macro-algae physiological characterization, the definition of the best conditions for their growth in ponds, including the evaluation of the resistance to CO2, NOx and SO2. In our study, the Life Cycle Assessment (LCA) methodology has been applied to evaluate the energy production from macro-algal biomass. We have developed a specific software (COMPUBIO) which can be used for an energetic, environmental or economic evaluation. We discuss here its application to estimate the energy balance for biofuel production from macro-algae, considering the overall process from CO2 capture from power plants to algae production and conversion. This study is aimed at establishing the feasibility of using seaweed as renewable-energy source and enhanced CO2 utilization. The flowchart includes the following steps: (1) flue gas (from power plants) recovery, (2) CO2 separation, (3) transport of CO2 or of the whole flue gas, (4) distribution of gas, (5) growing of algae, (6) collection of algae, (7) biofuel extraction from algae and processing. Although various separation technologies (monoethanolamineMEA, physical adsorption, cryogenics and membranes) are included into COMPUBIO, at this stage data relevant to MEA populate the database. This technology is widely used for industrial capture of CO2. It is based on the reversible uptake of CO2 by 2HOCH2 CH2 NH2 CO2 VHOCH2 CH2 NHCOO H3 NCH2 CH2 OH 1

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HOCH2CH2NH2MEA according to reaction (1). The CO2 uptake is favoured by high pressure and low temperature (290320 K, 15 MPa). CO2 can be released by lowering the pressure (0.1 MPa) and increasing the temperature (400430 K). The transport of either pure CO2 or flue gas (whenever macro-algae are resistant to the NOx and SO2 present in flue gas) is taken into account, and their distribution into algae ponds. For the production of fuels from the marine biomass, several technologies such as direct combustion, extraction with sc-CO2 or organic solvents, pyrolysis, gasification, liquefaction, anaerobic fermentation are included in COMPUBIO and used as necessary. These technologies are summarized below and the application of each of them is highlighted. Direct combustion (boiler and steam turbines) is conventionally adopted for producing energy from biomass. Large biomass power generation systems have an efficiency comparable with those of fossil fuel system, but the costs are higher because of the moisture content of biomass [11]. Among biological processes, anaerobic digestion, which produces methane and CO2, is best suited for high moisture-content herbaceous plants, marine crops and manure [12]. Among thermochemical processes pyrolysis, gasification and direct liquefaction can be used for all kinds of biomass, especially low-moisture herbaceous and woody. Pyrolysis converts (750 K and 0.10.5 MPa, in absence of air) the dried biomass into three phases: an oil-like liquid (bio-oil or biocrude), a carbon rich solid residue (charcoal) and a hydrocarbon rich gas mixture. Changing the temperature or the heating rate drives the reaction towards the promotion of charcoal, pyrolytic oil, gas or methanol. Fast-flash pyrolysis (low temperature, high heating rate, and short gas residence time) maximizes the yield of liquid products, while slow pyrolysis (low temperature, low heating rate) increases char. Fuel gas is maximized running the pyrolysis at high temperature, with low heating rate and long gas residence time. Pyrolysis has been applied to many products: solid waste, wood, agriculture crops and, more recently, aquatic biomass like micro-algae [13]. Gasification is a pyrolysis performed at high temperature in order to obtain only gas (Syngas) as product. Commercial gasifiers are available in a range of size and are run on a variety of fuels including wood, charcoal and agricultural waste. Recently, a low temperature catalytic gasification of biomass with a high moisture content (also algae) has been developed [14]. Liquefaction is a low temperature, high pressure thermochemical process which uses a catalyst to produce a liquid product from wet materials. Liquefaction, which is more expensive than pyrolysis, has been applied to recover liquid fuel from wet biomass and micro-algal biomass [15]. Among extraction techniques, the solvent extraction by using Soxhlet involves a repeated solvent distillation through a solid sample to remove the analyte of interest. This technique is sometimes very slow and requires the use of organic solvents which pose the problem of their disposal or recovery. A relatively new technique is the supercritical fluid extraction (SCFE). We have used supercritical carbon dioxide (scCO2) as extraction solvent. The scCO 2 extraction is quite advantageous, as CO2 is not toxic and its critical temperature is close to room temperature (304 K), and is

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suitable for the extraction of thermolabile compounds. Because of the low permeability and resistance of the cell membrane of algae, the efficacy of the scCO2 extraction depends on the strain used. Some of them require a pretreatment consisting on milling the algae for an efficient extraction of chemicals, biofuel, or lipids. Only scCO2 can be used for extraction or a co-solvent (methanol) can be added (373 K and 8 MPa) [9a,b,c]. In the former case, a dry residual mass is obtained which can be used for other purposes. COMPUBIO allows to assess the economic cost of CO2 utilization, the energetics of fuel production and to quantify the reduction of the atmospheric CO2 loading associated to the enhanced production of macro-algae as a source of biofuel. The software is of more general applicability and, by substituting some computing-blocks, could be used for assessing the potential of any kind of biomass, as renewable energy source.

2. Life cycle assessment The LCA methodology has been applied to compare several options for the enhanced fixation of CO2 for the production of algal biomass, using different kinds of algae (microand macro-) and various conversion technologies in order to select the process with best environmental, economic and energetic performance. 2.1. Methodology The SETAC (Society of Environmental Toxicology and Chemistry) guidelines have been used [10]. SETAC defines four phases for an LCA assessment: goal definition and scoping, inventory, impact assessment, interpretation (improvement) analysis. The LCA tool is under further development and improvement for including all kinds of biomass and possible extraction technologies. The life cycle considered includes the following steps: capture of CO2 from flue gases generated in power plants; transport of the whole flue gas or separated CO2; distribution of flue gas/CO2; algae production; algae harvesting; algae conversion to produce biofuel. 2.2. Goal definition and scoping Our study is aimed at assessing the potential of algal biomass as biofuel source and to evaluate the economic, energetic and environmental convenience. Therefore, the goal of the study is to establish the energetic benefits associated to the enhanced CO2 fixation in macro-algae, considering as boundary of the system the energy inputoutput. The functional unit has been fixed at 1 MJ of energy produced from algae. Our study allows a comparative evaluation of different production and conversion technologies using various algal strains with extension to other different kinds of biomass. The following assumptions have been made: the algae cultivation pond is situated at the seaside, preferably associated to a fishery; gas transport is in a range of 100 km; nutrients can be supplied with recycled wastewater from the fishery or from another source at a

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maximum distance of 5 km from the pond. The allocation close to a fishery avoids environmental impact issues and the integrated technology allows space (sea/land) optimal utilization. Moreover, the clean-up of water allows its recycle, with credits for the algae production process. 2.3. Energy analysis The flowchart traces the pathway along which the study will move; it contains per each stage the matter and energy balance. The life cycle stages are presented in Fig. 1. 2.3.1. Description of flowchart The flowchart integrates all processes from CO2 capture to biofuel extraction. The first stage is the CO2 emission from power plant and its capture. Power plants of various size (100600 MW) fed with various fuels (coal, oil, and natural gas) have been considered so that COMPUBIO can be used with different production-systems.

Fig. 1. Flowchart of the analyzed system.

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For CO2 distribution in ponds, two options have been considered: either direct flue-gas injection, or CO2 separationcompression and transport. The CO2 separation technologies included into COMPUBIO are: chemical absorption (MEA), physical adsorption, cryogenic separation, use of membranes. At the moment the software is populated with data relevant to the use of MEA. Next stage is algae production (COMPUBIO can be used with either micro-algae or macro-algae). The computing blocks include: Cultivation with temperature and irradiance control, aeration of ponds and stirring (only for micro-algae). Fertilisation. Different options have been taken into consideration: (i) nutrients supply, (ii) nutrients recovery from wastewater effluents, (iii) nutrients recycling from the wastewater solutions when gasification is used as the algae-conversion technology. The last two options make available an amount of nutrients sufficient for the algal growth. Effluent water from aquaculture plants, some municipal wastewater or breeding water can be used. Since the concentration of nutrients after algae growth is small enough to allow the water discharge into natural basins, the nutrient recovery is important not only for the internal energy/cost balance, but also for reducing the environmental impact of water-flows from another anthropic activity (fisheries, for example), with a credit to the algae-growing process. Harvesting of algae implies a quite different technology for micro- or macro-algae. Drying. It could be not required by some of the conversion technologies such as anaerobic digestion or liquefaction. In this study, it has been assumed that the drying, when necessary, is made by using solar energy. The final stage is the conversion of biomass. Different conversion technologies have been included into COMPUBIO, spanning from the direct combustion to other thermochemical or biochemical processes, making possible the selection of the best option with the biomass under study. 2.3.2. Collection and treatment of data Data relevant to alternative processes for algae treatment have been gathered, for a comparison of technologies (not all the technologies have had so far an application to aquatic biomass). In the inventory phase (Life Cycle Inventory, LCI), it is very important to describe the inputs and outputs for each step and each process. In the course of this study, we have verified that either data are not available for all processes or a discrepancy may exist between sources. Data for biofuel extraction from macro-algae, using either organic solvents or sc-CO2, have been collected through experiments carried out in our research group. The collected data can be summarized as reported below: Data on CO2 emission and capture have been obtained from databases [16], relevant research institutes [17,18] and scientific literature [19,20a,b,21].

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Data on algae production have been collected from agricultural research institutes [22a,b,c], farmer associations [23], scientific literature [24,2630] and personal communication of Italian research institutes [25,31]. Data on conversion of biomass have been provided by relevant industries [32], by literature [3339] and by experimental projects performed within our research group [41]. During the inventory stage, it has been necessary to ascertain the data quality in terms of geographical validity, time frame, and truthfulness of information. The quality of the data in LCI strongly affects the reliability of the whole study. 2.3.3. Processing of the collected data Usually the inventory process generates a long list of data which interpretation may be difficult. In this study, the data are presented in Inventory Tables of energy balance per each step of the production cycle. Calculations were carried out with Excel using the data reported in Table 1. In addition, we have developed a more complex computing model, using the software Visual BasicR 6.0 (see Figs. 2 and 3) which requires the presence of a writing interface for the application of the flowchart. After the compilation of the application in the bform codeQ mode using

Table 1 Relevant data collected for energy balance Process Gas transport CO2 distribution Algae production Direct injection CO2 separation Cultivation Nutrient supply Harvesting Drying Gasification Pyrolysis Liquefaction Anaerobic digestion Combustion Energy consumption (MJ) 0.0799a 1.672a 0b 2.15c 4.55c 0.85d, 5.5e 0f 5.95d 2.5g 6.711.9g 2.66h 11.9d Energy produced (MJ) References [20] [21] [15,22,34] [35] [34,31] [this work] [35] [32,33] [15,34] [38,39] [35]

Conversion technology

1520g 35f

The emission of power plant is assumed to be 0.9159 kg CO2/MJ if fed with coal; 0.7557 kg CO2/MJ if fed with oil; 0.5630 kg CO2/MJ if fed with natural gas. a Per kg CO2. b The energy consumption is zero as pressurized gas is used. c Per kg algae. d Per kg micro-algae. e Per kg macro-algae, referred to lagune harvesting. f Solar energy is used. g Per kg oil. h Per kg biomass.

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a)

b)

c)

d)

Fig. 2. The case of micro-algae: external nutrient supply(a) CO2 recovery; (b) direct flue gas injection; nutrient recovery; (c) CO2 recovery; (d) direct flue gas injection.

the specific language, it is possible to run the programme in the bform objectQ mode. With this model, it is possible to manage a large number of data making easy their interpretation.

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a)

b)

c)

d)

Fig. 3. The case of macro-algae: external nutrient supply(a) CO2 recovery; (b) direct flue gas injection; nutrient recovery; (c) CO2 recovery; (d) direct flue gas injection.

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The final value is calculated according to the choices in the writing interface and, changing the inputs, it is possible to compute the energy produced under different conditions. COMPUBIO manages the following options: CO2 emission: it is possible to choose the size and the capacity of the power plant. Gas used: it is possible to switch from the direct injection of flue gas to CO2 separation, compression and transport. CO2 distribution: two options of the ratio (CO2 fixed/amount of algae) are pre-set. Anyway, it is possible to vary the excess of CO2 pumped in the outdoor ponds over a wide range. Algae production: it is possible to select the type of algae (micro- or macro-) and the mode of nutrients supply for their growth (external nutrient supply, nutrient recycled, nutrient recovery from aquaculture, breeding and municipal wastewater). Conversion technology: data are available about the different conversion technologies of algal biomass. Table 1, Figs. 2 and 3 show the data elaboration process in the inventory analysis. Table 1 indicates the data collected for the energy balance. Here we have reported the most relevant data for each phase object of the study. Figs. 2 and 3 are examples of Visual BasicR 6.0 application to the calculation of net energy produced by growing algae. In Figs. 2 and 3 the micro-algae and macro-algae cases are presented, respectively. For both cases, a 600 MW power plant fed with coal is considered. Either CO2 separated using MEA (Figs. 2a and 3a) or flue gas is injected (Figs. 2b and 3b) in ponds; the ratio CO2 fixed/algae is 1:1 and the quantity pumped in ponds is in excess of five times; the fertilisation occurs either through nutrient supply (Figs. 2a,b and 3a,b) or nutrient recovery (Figs. 2c,d and 3c,d); the algae conversion process illustrated in the figures is the gasification for micro-algae and the anaerobic digestion for macro-algae, respectively. The calculated data (see Figs. 2a,b and 3a,b) show that the distribution of separated CO2 is energetically more favourable than the distribution of flue gas, which is in line with other studies [20b]. Also, if fresh nutrients have to be supplied, then the whole process will hardly produce energy, most likely it will consume energy (compare data in Figs. 2 and 3, ac for CO2 capture and bd for direct injection of flue gas).

3. Fuel extraction from macro-algae In our experimental work we have selected some macro-algae typical of the Adriatic or Jonian sea. In particular, the study has been carried out on two algae, Chaetomorpha linum (O.F. Mqller) Kqtzing (Cladophorales, Cladophoraceae) and the Pterocladiella capillacea (S.G. Gmelin) Santelices et Hommersand (Gelidiales, Rhodophyta). C. linum is dominant species in the bentopleustophytic population of Mar Piccolo in Taranto (Jonian sea), Italy, and very much present in the estuary of the Galeso river where it can reach a density of 3.6 kgdw/m2. P. capillacea, a very good agarophyte, can be found on the rocky substrates in the South Adriatic sea close to Bari, Italy and can reach a density of 0.15 kgdw/m2. These algae were never cultivated in vitro so far and, thus, we have ascertained the possibility of

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growing them on a large scale in a pond. The effects of several parameters such as: the dependence of the biomass production on nitrogen availability, ratio biomass/volume, salinity, temperature and irradiance were considered [40]. The two species have been selected because of their easy availability and low cost harvesting technology, their presence and vegetation all the year long, their ability to grow on a large-scale pond and high percent of compounds with a potential use as biodiesel [40]. Two extraction technologies were used such as solvent extraction and scCO2. Particular attention was dedicated to the preparation of samples, in order to ameliorate the efficiency of the process, and to the characterization of the lipidic content. The methodology for the extraction of biodiesel from algae using supercritical carbon dioxide was developed. A qualitative quantitative comparison of the extracts with those obtained using the organic solvent extraction was also carried out [40]. The scCO2 was shown to be more efficient and less costly. In a SITEC apparatus operated in batch at 313 323 K and 2530 MPa, the extraction of oil from algae was carried out using either scCO2 alone or added with methanol (1 mL) as co-solvent. The equipment can be used in continuous using only scCO2. In order to have an efficient extraction, it was necessary to pretreat the algae. In fact, if they were used as collected, no oil was extracted. Among the various techniques, grounding of dried (at 308 K) algae in liquid nitrogen was the most effective. The very fine solid obtained was extracted under the conditions specified above. Per each sample the amount of extracted oil was determined per kg of dry matter. The oil content varied from 7% to 20%. Then the oil was analyzed by GC-MS and its composition was determined. All extracted products were identified by GC-MS and the mass spectrum of each product was compared with that of an authentic sample used as standard. This allowed to identify the components of the oil and to calculate the heat content expressed as MJ/kg oil. Such value was checked through a combustion test. Such studies have shown that the morphological difference of the two algae is associated to a different lipid content, both quantitative and qualitative. In fact, in C. linum methyl myristate, methyl palmitate, methyl linoleate and methyl oleate are found, while P. capillacea contains besides methyl myristate and methyl palmitate, methyl arachidonate and methyl-all-cis-5,8,11,14,17 eicosanpentaenoate as major components. Studies are still in progress [41] for the complete characterization of the extract from algae grown under different light and temperature conditions and with different CO2 and nutrient supply.

4. Energetic balance LCA studies on biofuel production from terrestrial biomass (rapeseed oil) have already shown a convenient energy balance, despite the energy consumption in the cultivation and processing stages, and much lower emissions than fossil fuels [42,43]. The energetic yield of micro-algae has also been reported [20]. Similar studies on macro-algae are not available. In this study, we have considered in particular macro-algae and developed a software that may be used for several options. The global balance of the process of production of biofuel takes into account all the energy inputs and the produced amounts of energy.

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Separate calculation modules deal with the amount of energy relevant to the six sections illustrated in Fig. 1. As reported in Eq. (2), the net energy (Enet) produced is the sum of a number of terms relevant to the gained and used energy specified in the second member of the equation. Enet Eric Eb Ers Ets EsaEscr EdEdV Ec Enu Eh Edr Epr EscEso Ees 2

The first three terms of the second member of Eq. (2) represent the gained energy, while others indicate the spent energy. The first term, Eric, is the energy that may be recovered as heat from the hot flue gases emitted from a power plant. If cooled gases are considered, this amount will be zero. Eb is the energy associated to the extracted biofuel and Ers is the energy of the residual solid biomass (or tars). The other terms are, in general, relevant to energy spent in the process. Following the flowchart in Fig. 1, the section bseparation and transportQ includes the separation energy using MEA or cryogeny (in Eq. (2), Esa, indicates the energy when MEA is used as separation phase, Escr is the energy of separation by cryogeny). Ets is the transport energy. Section 3 of Fig. 1 is relevant to the distribution: either separated CO2 or the entire flue gas are considered here. In Eq. (2), Ed represents the energy of distribution of separated CO2 and EdV is the energy for the distribution of the entire flue gas. Section 4 in Fig. 1 is relevant to the production of algae. The algae cultivation energy is indicated as Ec in Eq. (2). Algae need nutrients (N, P, microelements) to which the energy Enu is associated. A variance analysis has shown that if nutrients are added as fresh chemicals to the pond, the overall energetic balance may be negative. Therefore, in order to avoid such huge amount of energy input, either effluent water from aquaculture plants should be used, or some selected municipal waters. The treated water can be either recirculated to the fishpond or emitted into natural basins without paying any penalties. Such use of effluent water, by the way, generates a credit to the process that may be ultimately taken into account in its economic evaluation. In the phase of growing, macro-algae do not need a vigorous stirring as micro-algae. This difference introduces a credit for the macroalgae system when compared to micro-algae. The energy associated to algae harvesting is Eh. Macro-algae grow either on a solid substrate or free-floating in water. In the former case it is necessary to cut the algae, that slightly rises the energy consumption. With freefloating algae, harvesting can be made by simply rising a net installed in the pond, with a large energy saving with respect to micro-algae, which need filtration for their separation. The following section in Fig. 1 is relevant to algae treatment for biofuel production. According to the conversion process, either wet or dry algae can be used. Some technologies as anaerobic fermentation or liquefaction directly use wet algae. Drying, if required, is made by using solar energy or recovered heat and the associated energy is reported in Eq. (2) as Edr. Also, dried algae may or may not need to be pretreated for biofuel extraction. In case pretreatment is needed (see above), the associated energy is Epr in Eq. (2). Among biofuel extraction techniques, the extraction with scCO2 (Esc) or organic solvents (Eso) has been considered here. Ees is the energy for processing the extracted biofuel. The utilization of scCO2 as solvent for biofuel extraction appears quite interesting,

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as captured carbon dioxide can be used to this end, making the whole process solvent-free, and avoiding, thus, the production of waste solvents. The whole balance shows that energy production from marine biomass is an attainable target with the available technologies. In general, the obtained biofuel is too expensive yet if it is compared to fossil fuel without emission capture [20b]. Should benvironmental costsQ be considered enhanced CO2 fixation into marine biomass as a technology for carbon recycling and energy production may become an economic route to reducing the CO2 emission [44].

5. Conclusions In this paper we have presented the preliminary results of an ongoing study on the utilization of macro-algae for enhanced CO2 fixation for the production of biofuel. We have developed a software (COMPUBIO) that allows to calculate the net energy of the process using an LCA approach. The LCA study performed in the present work demonstrates that there is a potential energy benefit associated to recycling carbon by enhanced fixation of CO2 by macro-algae, if it is associated with the use of effluent water as source of nutrients. The net energy gain depends on the conversion technology. In the best case considered so far, macro-algae can generate a net energy of the order of 11,000 MJ/tdryalgae compared to 9500 MJ/t relevant to micro-algae gasification. Besides the energy balance that is encouraging, the economic balance and the emissions are under evaluation for completing the study. The ensemble of energetic, economic and environmental assessments may be useful for supporting political decisions. Being preliminary results on the energy balance encouraging, the inventory of emissions associated to biofuel production is being completed with their classification into impact categories to assess the global environmental impact of the whole cycle of production of biofuel. The versatility of COMPUBIO that can be applied to different types of biomass and can take into consideration various technologies is useful for performing a comparative LCA between fossil fuel and biofuel derived from different renewable sources.

Acknowledgements This work was done with the financial support of MIUR-FIRB 2001, Project RBAU017RWX.

References
[1] IEA Report, Carbon Dioxide Utilization: evaluation of specific biological processes which have the capability of directly utilising high concentrations of carbon dioxide as found in the flue gas streams from power generation plant, 1994. [2] a) M. Aresta (Ed.), Carbon Dioxide Recovery and Utilisation, Kluwer Publ., 2003; b) M. Murakami, M. Ikenouchi, The biological CO2 fixation and utilization project by RITE (2), Energy Conversion and Management 38 (1997) S475 S479 (Suppl.);

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M. Aresta et al. / Fuel Processing Technology 86 (2005) 16791693 c) J.R. Benemann (Ed.), CO2 mitigation with microalgae systems, Energy Conversion and Management, vol. 38 Suppl., 1997, pp. S475 S479. L.M. Brown, Uptake of carbon dioxide from flue gas by microalgae, Energy Conversion and Management 37 (68) (1996) 1363 1367. M. Olaizola, E.O. Duerr, D.W. Freeman, Effect of CO2 enhancement in an outdoor algal production system using Tetraselmis, Journal of Applied Phycology 3 (1991) 363 366. J.C. Goldman, Outdoor algal mass cultureI applications, Water Research 13 (1979) 1 19. J. Sheehan, T. Dunahay, J. Benemann, P. Roessler. A Look Back at the U.S. Department of Energys Aquatic Species ProgramBiodiesel from Algae. National Renewable Energy Laboratory, Golden, CO, 1998. 80401 NREL/TP-580-24190. E.W. Wilde, J.R. Benemann, Bioremoval of heavy metals by the use of micro-algae, Biotechnology Advances 77 (1993) 781 812. K. Gao, K.R. Mckinley, Use of macro-algae for marine biomass production and CO2 remediation: a review, Journal of Applied Phycology 6 (1994) 45 60. a) M. Aresta, A. Dibenedetto, I. Tommasi, E. Cecere, M. Narracci, A. Petrocelli, C. Perrone, The use of marine biomass as renewable energy source for reducing CO2 emissions, October 2002. Elsevier, Special Issue Dedicated to GHGT-6, Kyoto; b) M. Aresta, Energy from marine biomass, Polish Journal of Environmental Studies II (Suppl. I) (2002) 35 40; c) M. Aresta, A. Dibenedetto, G. Barberio, Utilisation of macroalgae for enhanced CO2 fixation and energy production, Preprints of Papers-American Chemical Society. Division of Fuel Chemistry 49 (1) (2004) 348 349. SETAC, Bruxell. Guidelines for Life-Cycle Assessment: A Code of Practice. Consoli, Allen, Boustead, Fava, Franklin, Jense de Oude, Parrish, Perriman, Postelthwaite, Quay, Sequin, and Vigon, 1993. A. DemirabaY, Biomass resource facilities and biomass conversion processing for fuels and chemicals, Energy Conversion and Management 42 (2001) 1357 1378. E.A. Laws, Photosynthetic efficiency optimization studies with the macroalga Gracilaria tikvihae: implications for CO2 emission control from power plants, Bioresource Technology 37 (1991) 25 33. O. Onay, O.M. Kockar, Slow, fast and flash pyrolysis of rapeseed, Renewable Energy 28 (2003) 2417 2433. D.C. Elliott, L.J. Sealock, Chemical processing in high-pressure aqueous environments: low temperature catalytic gasification, Trans IchemE 74 (1996) 563 566. S. Sawayama, T. Minowa, S.-Y. Yokoyama, Possibility of renewable energy production and CO2 mitigation by thermochemical liquefaction of microalgae, Biomass and Bioenergy 17 (1999) 33 39. Sima Pro Database. Pre Consultants. ` EMEP/CORINAIR, Emission Inventory Guidebook, 3rd edition, October 2002, Technical report no. 30, Published by EEA (European Environment Agency). P. Spath, M.K. Mann, Capturing and sequestering CO2 from a coal-fired power plantassessing the net energy and greenhouse gas emissions, NREL, 1997. K. Tahara, T. Kojima, A. Inaba, Evaluation of CO2 payback time of power plants by LCA, Energy Conversion and Management 38 (1997) S615 S620 (Suppl.). a) K.L. Kadam, Environmental implications of power generation via coal-microalgae cofiring, Energy 27 (2002) 905 922; b) K.L. Kadam, Power plant flue gas as source of CO2 for microalgae cultivation: economic impact of different process options, Energy Conversion and Management 38 (1997) S505 S510 (Suppl.). G. Gottlicher, R. Pruschek, Comparison of CO2 removal systems fossil-fuelled power plant processes, Energy Conversion and Management 38 (1997) S173 S178 (Suppl.). FAO: a) V.S.K. Chennubhotla, Status of seaweed culture in India. b) Manual on seaweed culture: pond culture of Caulerpa and Gracilaria, 1988, c) The artificial cultivation of Gracilaria, 6, 246. I.R. Richards, BAFBOBritish Association for Bio Fuel and OilLevington Agriculture Report June 2000. Energy balances in the growth of oilseed rape for biodiesel and of wheat for bioethanol, 2002. P.S. Lavery, A.J. McComb, The nutritional eco-physiology of Chetomorpha linum and Ulva rigida, Botanica Marina 34 (1991) 251 260.

[3] [4] [5] [6]

[7] [8] [9]

[10] [11] [12] [13] [14] [15] [16] [17] [18] [19] [20]

[21] [22] [23] [24]

M. Aresta et al. / Fuel Processing Technology 86 (2005) 16791693

1693

[25] C. Perrone, Department of Plant Biology and Pathology, University of Bari. Personal communication. [26] E. Marinho-Soriano, C. Morales, W.S.C. Moreira, Cultivation of Gracilaria (Rhodophyta) in shrimp pond effluents in Brazil, Aquaculture Research 33 (2002) 1081 1086. [27] M. Troell, C. Halling, A. Nilsson, A.H. Buschmann, N. Kautsky, L. Kautsky, Integrated marine cultivation of Gracilaria chilensis, (Gracilariales, Rhodophyta) and salmon cages for reduced environmental impact and increased economic output, Aquaculture 156 (1997) 45 61. [28] A. Schuenhoff, M. Shpigel, I. Lupatoch, A. Ashkenazi, F.E. Msuya, A. Neori, A semi-recirculating, integrated system for the culture of fish and seaweed, Aquaculture 221 (2003) 167 181. [29] E.J. Olguin, S. Galicia, G. Mercado, T. Perez, Annual productivity of Spirulina (Arthrospira) and nutrient removal in a pig wastewater recycling process under tropical conditions, Journal of Applied Phycology 15 (2003) 249 257. [30] Josianne G. Stottrup, Lesley A. McEvoi (Eds.), Live Feeds in Marine Aquaculture, Blackwell Science, Oxford, 2003. [31] M. Lenzi, ICRAM, Roma, Italy. Personal communication. [32] K.W. Morris, Fast pyrolysis of bagasse to produce biooil fuel for power generation, International Sugar Journal 103 (1230) (2001) 259 263. [33] Q. Wu, J. Dai, Y. Shiraiwa, G. Sheng, J. Fu, A renewable energy sourcehydrocarbon gases resulting from pyrolysis of the marine nanoplanktonic alga Emiliana huxleyi, Journal of Applied Phycology 11 (2) (1999) 137 142. [34] S. Sawayama, S. Inoue, Y. Dote, S.-Y. Yokoyama, CO2 fixation and oil production through microalga, Energy Conversion and Management 36 (69) (1995) 729 731. [35] T. Minowa, S. Sawayama, A novel microalgal system for energy production with nitrogen cycling, Fuel 78 (1999) 1213 1215. [36] P.C.K. Cheung, Temperature and pressure effects on supercritical carbon dioxide extraction of n-3 fatty acids from red seaweed, Food Chemistry 65 (1999) 399 403. [37] R.L. Mendes, J.P. Coelho, H.L. Fernandes, I.J. Marrucho, J.M.S. Cabral, J.M. Novais, A.F. Palavra, Supercritical carbon dioxide extraction of hydrocarbon from the microalga Botryococcus braunii, Journal of Applied Phycology 6 (1994) 289 293. [38] X.Y. Briand, P. Morand, Anaerobic digestion of Ulva sp. 1. Relationship between Ulva composition and methanisation, Journal of Applied Phycology 9 (1997) 511 524. [39] K. stgaard, M. Inderggard, Carbohydrate degradation and methane production during fermentation of Laminaria saccharina (Laminariales, Phaeophyceae), Journal of Applied Phycology 5 (1993) 333 342. [40] CNR AGENZIA, 2000 Project CNRC008EBF. [41] M. Aresta, A. Bottalico, M. Carone, I. Delle Foglie, A. Dibenedetto, C. Perrone, Proceedings of the CONISMA Meeting, Italy, September 2004. [42] IFEU-Institut fqr Energie- und Umweltforschung, S.O. Gartner, G.A. Reinhardt, Life Cycle Assessment of Biodiesel: Update and New Aspects, May 2003. Final report, Project no. 530/025. [43] C. Spirinckx, D. Ceuterix, Biodiesel and fossil fuel: comparative LCA, The International Journal of Life Cycle Assessment 1 (3) (1996) 127 132. [44] a) M. Aresta, A. Dibenedetto, G. Barberio, Life Cycle Assessment of fuel production from macro-algae: evaluation of the net energy gain and CO2 atmospheric loading reduction, GHGT-7, 59 September, Vancouver, BC, Canada, 2004; b) M. Aresta, Dibenedetto A., Barberio G., in press.