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    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 BarberioIAMC, 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 anenergetic 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)

    0378-3820/$ - see front matterD 2005 Elsevier B.V. All rights reserved.

    doi:10.1016/j.fuproc.2005.01.016

    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 CO 2;

    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: [email protected] (M. Aresta).

    Fuel Processing Technology 86 (2005) 1679 1693www.elsevier.com/locate/fuproc

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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 respectto 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 macro-

    algae for biofuel production integrating the capture of CO2 from continuous point sources

    (power plants, industries), its purification, distribution with uptake by macro-algae andtheir 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

    2HOCH2CH2NH2 CO2VHOCH2CH2NHCOOH3NCH2CH2OH 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 (lowtemperature, 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 andmicro-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 scCO2 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 (micro-

    and 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 havebeen 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 ofthe 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 ofvarious 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 thealgae-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 importantto 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 Energyconsumption (MJ)

    Energy produced (MJ)

    References

    Gas transport Direct injection 0.0799a [20]

    CO2 separation 1.672a [21]

    CO2 distri bution 0b

    Algae production Cultivation 2.15c [15,22,34]

    Nutrient supply 4.55c [35]

    Harvesting 0.85d, 5.5e [34,31]

    Drying 0f [this work]

    Conversion technology Gasification 5.95d [35]

    Pyrolysis 2.5g 1520g [32,33]

    Liquefaction 6.711.9g 35f [15,34]

    Anaerobic digestion 2.66h [38,39]

    Combustion 11.9

    d

    [35]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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    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.

    a) b)

    d)c)

    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.

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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 technologiesof 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 CO2fixed/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 orJonian 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 scCO 2alone 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 valuewas 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 Esa Escr Ed EdV Ec Enu Eh

    Edr Epr Esc Eso 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 andtransportQ 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 plantsshould be used, or some selected municipal waters. The treated water can be either re-

    circulated 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 macro-

    algae 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 free-

    floating 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. Sometechnologies 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. Wehave 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 biofuelproduction 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.

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