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This document compares different microalgae liquid biofuel production pathways based on energetic, economic, and environmental criteria. It evaluates the techno-economic viability of three emerging pathways: hydrothermal liquefaction (HTL) of wet biomass into bio-crude, secretion of oils from microalgae directly into the growth medium, and secretion of alkanes from microalgae for use as a drop-in fuel. While these pathways have technological challenges, they also show potential advantages over traditional lipid extraction and conversion to biodiesel, such as increased total biodiesel yield from HTL or better energy and environmental performance from secretion of oils or alkanes.
This document compares different microalgae liquid biofuel production pathways based on energetic, economic, and environmental criteria. It evaluates the techno-economic viability of three emerging pathways: hydrothermal liquefaction (HTL) of wet biomass into bio-crude, secretion of oils from microalgae directly into the growth medium, and secretion of alkanes from microalgae for use as a drop-in fuel. While these pathways have technological challenges, they also show potential advantages over traditional lipid extraction and conversion to biodiesel, such as increased total biodiesel yield from HTL or better energy and environmental performance from secretion of oils or alkanes.
This document compares different microalgae liquid biofuel production pathways based on energetic, economic, and environmental criteria. It evaluates the techno-economic viability of three emerging pathways: hydrothermal liquefaction (HTL) of wet biomass into bio-crude, secretion of oils from microalgae directly into the growth medium, and secretion of alkanes from microalgae for use as a drop-in fuel. While these pathways have technological challenges, they also show potential advantages over traditional lipid extraction and conversion to biodiesel, such as increased total biodiesel yield from HTL or better energy and environmental performance from secretion of oils or alkanes.
Comparison of various microalgae liquid biofuel production pathways
based on energetic, economic and environmental criteria
F. Delrue a, , Y. Li-Beisson b,c,d , P.-A. Setier e , C. Sahut b,c,d , A. Roubaud e , A.-K. Froment e , G. Peltier b,c,d a CEA, Direction de la Recherche Technologique, Laboratoire des Technologies de la Biomasse, CEA Cadarache, Saint-Paul-lez-Durance F-13108, France b CEA, Direction des Sciences du Vivant, Institut de Biologie Environnementale et de Biotechnologie, CEA Cadarache, Saint-Paul-lez-Durance F-13108, France c CNRS, UMR 7265 Biologie Vgtale et Microbiologie Environnementale, Saint-Paul-lez-Durance F-13108, France d Aix Marseille Universit, UMR 7265 Biologie Vgtale et Microbiologie Environnementale, Saint-Paul-lez-Durance F-13108, France e CEA, Direction de la Recherche Technologique, Laboratoire des Technologies de la Biomasse, 17 Rue des Martyrs, Grenoble F-38054, France h i g h l i g h t s " Techno-economic evaluation of alternative microalgae biodiesel production pathways. " Technological breakthrough needed but high potential for these pathways. " Hydrothermal liquefaction is of interest for processing defatted microalgae. " Better energetic and environmental criteria for secretion of oil or alkane. a r t i c l e i n f o Article history: Received 26 December 2012 Received in revised form 21 February 2013 Accepted 22 February 2013 Available online 4 March 2013 Keywords: Oil secretion Algal biofuel Alkane secretion Techno-economic evaluation a b s t r a c t In view of the increasing demand for bioenergy, in this study, the techno-economic viabilities for three emerging pathways to microalgal biofuel production have been evaluated. The three processes evaluated are the hydrothermal liquefaction (HTL), oil secretion and alkane secretion. These three routes differ in their lipid extraction procedure and the end-products produced. This analysis showed that these three processes showed various advantage s: possibility to convert the defatted microalgae into bio-crude via HTL thus increasing the total biodiesel yield; better energetic and environmental performance for oil secretion and an even increased net energy ratio (NER) for alkane secretion. However, great technological breakthroughs are needed before planning any scale-up strategy such as continuous wet biomass pro- cessing and heat exchange optimization for the HTL pathway and effective and sustainable excretion for both secretion pathways. 2013 Elsevier Ltd. All rights reserved. 1. Introduction Fossil fuel depletion and global warming are pressing the need on todays society to look for alternative sources of energy. In this context, fuels derived from biomass (biofuels) are renewable and versatile (including biohydrogen, bioethanol, biodiesel, kerosene, etc.), show characterist ics of traditional petroleum fuel thus can be used to replace part of the petroleum transportation fuels. Due to its high biomass productivity , and not competin g with crops for agricultu ral land use, microalgae have emerged as one of the most attractive platforms for biofuel production (Wijffels and Barbosa, 2010 ). Algae biodiesel 1 product ion from microalgae ob- tained after lipid extraction and conversion is the most studied algae biofuel . A basic research in Scopus showed 750 results for algae bio- diesel, 106 results for algae bioethanol, 65 results for algae bio- hydrogen and 31 results for algae hydrothermal liquefaction (search perform ed on the 5th of September, 2012). The feasibilit y and constraints for biodiesel production from li- pid extraction of microalgae have been evaluated in a previous study based on an economic, sustainability and energetic analysis (Delrue et al., 2012 ). Besides this common pathway (i.e. biodiesel production), latest technological as well as biological advances have opened door to several alternative routes. These break- throughs include (i) the setup of an hydrothe rmal liquefaction (HTL) way to convert biomass to bio-crudes directly (Dote et al., 1994); (ii) the nding that cellular oils can also be secreted into the medium thus bypassin g the need to harvest and dry biomass (Liu et al., 2011 ); and (iii) microalgae also possess the capacity to synthesize and secret a range of alkanes/alkene s thus allowing 0960-8524/$ - see front matter 2013 Elsevier Ltd. All rights reserved. http://dx.doi.org/10.1016/j.biortech.2013.02.091
Corresponding author. Tel.: +33 4 42 25 35 56.
E-mail addresses: orian.delrue@cea.fr, fdelrue@yahoo.fr (F. Delrue). 1 After lipid extraction two main processes are considered leading to two biofuel with similar characteristics but different names: hydrotreating (renewable diesel or green diesel) and transesterication (biodiesel). In this work, the resulting biofuel is named indiscriminately biodiesel. Bioresource Technology 136 (2013) 205212 Contents lists available at SciVerse ScienceDi rect Biore source Technology j our nal homepage: www. el sevi er . com/ l ocat e/ bi or t ech production of drop-in fuel avoiding the expensive chemical pro- cessing step (i.e. transesterication) (Bachofen, 1982 ). These new inventions/d iscoveries however have not yet been evaluated from a techno-economi c point of view. In this study, the potentials of all three processes have been analyzed. In order to compare the future potential offered by these algae biofuel production pathways, all the technologic al barriers of these processes have been assumed to be overcome (i.e. continuo us bio-crude production by HTL, mic- roalgae strain capable of directly excreting natural lipids). A Monte-Carlo approach has been adopted since uncertainties re- main about future developments of these pathways. These three different pathways have been compare d to the wet lipid extractio n pathway [with anaerobic digestion (AD) of the lipid extractio n res- idues], which has been published previousl y (Delrue et al., 2012 ). HTL is a promising process that converts wet biomass directly into a bio-crude. This technology has led to increasing interest among the scientic community since the rst experiment con- ducted on Botryococc us braunii (Dote et al., 1994 ). The major advantages associate d to this HTL process include direct processin g of wet biomass, its high yields (e.g. Biller et al., 2011; Jena et al., 2011) and the possibility to recover part of the nutrients in the aqueous phase (Biller et al., 2012 ). Nonetheless, one of the most obvious drawbacks is its requiremen t for high pressure (100 200 bars) and more importantl y moderate to high temperat ure (300370 C) which can potential ly lead to a high energy demand. Thus one of the focuses of the current study is to propose a model evaluating this process with specic attention to the energetic balance. Evidence that microalgae can accumulate large quantity of oil in their biomass is a well-known phenomeno n (Brennan and Owende, 2010 ); thus most techno-economi c analyses reported so far have focused on evaluation of this pathway. Lipid secretion has long been studied in higher plants, and has also been observed in microorgan isms including microalgae for example cyanobac te- ria (Liu et al., 2011 ) and B. braunii (Bachofen, 1982 ). But until re- cently, the molecula r players involved in lipid (alkanes or oils) synthesis and secretion have been discovered (Schirmer et al., 2010; Liu et al., 2011 ). The authors have further demonstrat ed that microorgan isms (cyanobacteria or Escherichia coli ) can be engi- neered to produce and secrete fatty acids or alkanes into its extra- cellular media via genetic engineering. These proof-of-con cept engineering studies have raised questions on how/if the lipid secretion pathway would be economically viable, and what will be the most costly steps associated. Classical algal liquid biofuel production pathway involves mass cultivation, biomass harvestin g and drying, lipid extraction and nally chemical conversion of the lipid extracted for forma- tion of biofuel. In theory, lipid secretion by algal cells will allow direct recovery of lipids without the need for biomass harvestin g and lipid extraction, which are energy-intensive steps (Delrue et al., 2012 ). Thus, direct secretion of these highly energetic mol- ecules from microalgae (lipids or alkanes) would be highly desir- able in industrial processes (Wijffels and Barbosa, 2010 ). The molecules excreted in the cultivatio n media can then be easily recovered and converte d into biodiesel. Since lipids are a general term and encompass a large variety of organic molecule s which are soluble in organic solvent but usually not in water, depending on the lipid species produced (triacylglycerols or alkanes), differ- ent downstream processing is required for being used as fuels. Thus, in this study, the lipid secretion pathway have been evalu- ated in two parts: oil secretion (requiring the chemical conversio n of lipids into biodiesel) and alkane secretion (as a ready-to- use fuel). The key parameters inuencing the results of the processes evaluated have also been identied based on a global sensitivity analysis. 2. Methods 2.1. Techno-ec onomic model methodology The methodology is based on a previously published model for biodiesel production (Delrue et al., 2012 ). Four model outputs are used to evaluate the whole process of algae biofuel production: the Net Energy Ratio (NER): the total primary energy consumed (including chemical s but excluding buildings) divided by the total energy produced during the process; the production cost : total operating cost over a year divided by the annual biofuel energy production in Giga Joule (GJ) of biodiesel ; the Green House Gas (GHG) emission rate : the total annual GHG emission s expressed in kgCO 2 -eq (including chemical s and the use of the biofuel but excluding buildings) divided by the total annual energy produced in GJ; the Water Footprint : the annual water consumption in L divided by the total annual energy produced in GJ. Each parameter of the model is dened by its minimum and maximum values between which they vary in a random manner. The objective here is to account for the uncertainty on the param- eters value due to the need for scale-up and technologic al breakthr oughs. One run of the model is made of 25,000 samples resulting in a large pool of probable results for the four model outputs. These re- sults are then sorted using the parameters Y 25% and Y 75% dened as follow: Y 25% is the output value under which 25% of the output values is containe d (rst quartile). Y 75% is the output value under which 75% of the output values is containe d (third quartile). The microalgae biofuel pathways are evaluated and compare d using these Y 25% and Y 75% parameters and the mean output value for the four outputs: the NER, the production cost, the GHG emis- sion rate and the water consumptio n. Addition ally, Saltelli-Sobol indices S i (Saltelli, 2002 ) are used to estimate the inuence of each parameter on the four outputs. For each paramete r of the model, four indices S i are calculated (S i,NER , S i,cost , S i,GHG , S i,water ) representing the paramete rs inuence over the outputs. The sum of S i for each output is equal to one. Then, if S i,NER = 0.25 for Convertible Lipid (CL) content for the wet lipid extractio n pathway (example taken from Delrue et al., 2012 ), it means that the CL content inuences the NER by 25% . These indices are evaluated with a numerical method requiring a Monte-Carlo sampling. Details of the calculations for this global sensitivit y analysis method can be found in the article cited above (Saltelli, 2002 ). 2.2. System description The production of algal biodiesel is assumed to be located in a sunny area in France (SouthEast), with sources of CO 2 from ue gases and wastewater at disposal. These assumptions may be con- sidered as optimistic but have been chosen to simplify the model. However , a recent study by Fortier and Sturm (2012) gives some strength to this approach. They demonstrat ed that 29% of the Kan- sas liquid fuel demand could be met with commerc ial-scale algal biodiesel production plants fed with wastewater whereve r it is possible. The production infrastructu res are included in the economic estimations but are not considered in the energy balance (NER) 206 F. Delrue et al. / Bioresource Technology 136 (2013) 205212 and in the GHG emission rate and water consumptio n calculatio ns. The total volume of microalgae cultivation is set at 1,000,000 m 3 which is equivalent to a cultivation surface of 333.3 hectares of 30 cm-depth raceways. This volume has been considered as a rea- sonable projection of what would be an industrial facility of micro- algae cultivation dedicated to biofuel production. Mass balance calculations for nutrients are based on the microalgae formula fromGrobbelaar (2004): CO 0.48 H 1.83 N 0.11 P 0.01 . The water rell is as- sumed to be done using wastewater . The exceedin g nutrient de- mand is delivered by additional nutrients (ammonium diphosphate for phosphorus and anhydrous ammonia for nitrogen). The process line for harvesting and dewateri ng (decanter, thick- ener and belt lter press) is based on the biodiesel model results within the innovative scenario (Delrue et al., 2012 ). Water is recycled from the harvesting and dewateri ng steps to the cultivation step. The recycled fraction of water is estimated by the model using the recycle fraction (between 0.8 and 0.99) for each steps where water is removed from the cultivation media (i.e. decantation , thickenin g and dewatering through belt lter press). All prices have been converted to Euros based on an ex- change rate as the date of April 2011. For example, conversions of dollars into Euros have been made based on an exchange rate of 1.42 /$. Costs of electricity and natural gas are set at 0.0687 and 0.0322 /kWh, respectivel y. These values are based on the 2010 data of the Eurostat database. Nitrogen and phosphorus nutrients prices are xed at 0.73 /kg of N and 1.02 /kg of P, respectively (National Agricultural Statistics Service, 2011). A car- bon credit in the range (1050) /ton of CO 2 and a credit range of (0.040.12) /m 3 of wastewater have been attributed. The production cost is calculated as the ratio between the total operating cost over a year and the annual energy production in GJ. The total operating cost is the sum of the operating cost (utilities, labour and other costs) and the xed cost (method from Chauvel et al., 2001 ). The xed cost is calculated from the depreciabl e cap- ital cost (overnight construction) that includes 55% of the capital cost for the general maintenanc e, storage, engineering and spare parts costs, licence fees (xed at 0.5 M), initial expenses at 2% of the capital cost and process start-up cost at 25% of the operating cost. The calculation is based on annuities of 20 years, discount rate of 8% and 7% of the capital cost per year for maintenanc e cost, taxes, insurance and business expenses. More detailed information on the model can be found in the previous publication (Delrue et al., 2012 ). Table 1 shows the parameters used for the system denition. 2.3. A specic model for hydrothermal liquefactio n The model for HTL has been built around the data collected from several papers (Ross et al., 2010; Jena et al., 2011; Frank et al., 2012; Vardon et al., 2012 ) (see Supplement al material for more information). Table 2 presents the paramete rs of the model and Fig. 1 shows the process owsheet. For the capital cost estima- tion of the reactors and its devices, the pressure has been set at 200 bars (capital cost calculations available in the Supplemental material). The model assumed that the reactors allow continuous hydrothermal liquefacti on, even if the design of such reactor is not yet known. The separation and recovery of the oil is another major challenge that has to be overcome. In this model, the techno- logical breakthrough allowing the oil recovery has been assumed. And the separation processes of oil, water and solids have been in- cluded in the cost of the reactors and that this technolo gical has been assumed. Recirculation of the aqueous phase which contains high amount of nutrients is assumed. Experimental tests by Biller et al. (2012) have shown that it is feasible if diluted (by wastewa ter in the model). Minimum and maximum of the recycling fraction for nitrogen and phospho rus have been set at 10% and 30%, respec- tively which are conservative gures based on the work from Ross et al. (2010). They reported that between 10% and more than 50% of the nitrogen can be retrieved in the aqueous phase depending on the catalysts used (KOH, Na 2 CO 3 , acetic acid or formic acid), the temperature (300 or 350 C) and the species (Chlorella vulgaris or Spirulina platensis ). The energy consump tion of the HTL process has been assumed to be equal to the energy needed to heat the solution up to the pro- cess temperature (electricity demand is assumed to be negligible). The heat demand is calculated using the specic heat capacity of water at constant pressure C p varying with temperature (calcula- tions detailed in the Supplement al material ). The very high heat demand from HTL is a major drawback. Therefore, a spiral tube heat exchanger has been integrated in the system. The liquids coming out of the HTL reactor (bio-crude and aqueous phase) is used to pre-heat the biomass coming in the reactor. The char resulting from the HTL of microalgae is burnt in a boi- ler to produce heat for the process. The characteristics of the boiler burning the biogas from AD in the previous model (Delrue et al., 2012) have also been used here (efciency between 0.8 and 0.89, cost between 8600 and 23,900 /MW) since this kind of units can re a variety of fuels including coal, oil, gas, biomass and waste (EPA, 2002 ). The gas produced during the liquefaction of microal- gae is mainly composed of CO 2 (between 84% and 96% of the gas produced according to Jena et al., 2011 ) and cannot be burnt in a boiler. The bio-crude is upgraded through a hydrotreating process (hy- dro-deox ygenation, HDO). The characteri stics of this HDO step is similar to the previous model (Delrue et al., 2012 ): electricity con- sumption between 0.0008 and 0.0024 kWh/kg of bio-crude, gas consump tion between 0.156 and 0.469 kWh/kg of bio-crude, cost between 70 and 210 /ton of bio-crude/year . Similar H 2 consump- tion (between 0.01 and 0.02 /kg of bio-crude) has been assumed although the hydro-conv ersion of HTL bio-crude to diesel fuel will certainly require less H 2 . 2.4. Specic models for secretion 2.4.1. Concept of secretion of energetic molecules Direct secretion of molecules useable as an energy source (oil, alkane) by microalgae (Fig. 2) is of great interest since the steps of biomass harvesting and extraction of these molecules from in- side the cells are very energy intensive (Wijffels and Barbosa, 2010). From a previous work (Delrue et al., 2012 ), these steps were found to be responsible for 42% on average of the total energy con- sumption in the wet extraction pathway and 67% on average for the reference pathway (based on a cultivatio n in raceways and a dry extraction using hexane). Concerning oil secretion , it has been observed in the yeast Saccharomyc es cerevisiae which interestingly takes mainly place during logarithmic growth (Scharnewski et al., 2008). Recently, secretion of fatty acids by cyanobac terium Syn- echocysti s sp. has also been achieved by genetic engineering (Liu et al., 2011 ). These results showed that oil secretion in microalgae seems feasible and promising. Secretion of hydrocarbons directly into the medium by the microalga B. braunii has been well known for more than 150 years (Bachofen, 1982 ). However, the very slow growth rate of B. braunii limits its capacity as a platform for fuel production (maximum of 0.114 gDWB/L/d) (Sakamoto et al., 2012 ). Alkane production in cyanobac teria has also been widely observed through biologica lly conversio n of carbohydrat es (Schirmer et al., 2010 ) and gives cred- its to this approach in microalgae. F. Delrue et al. / Bioresource Technology 136 (2013) 205212 207 A major drawback in secreting oil or alkane to the medium is bacterial/fungi contaminat ion which has to be avoided at all cost since they will likely consume the excreted lipids as carbon sources. In order to ensure an axenic culture, the use of closed sys- tems (PBR in the model) is thus mandatory. 2.4.2. Oil secretion The model of oil secretion (as shown in Fig. 3) is based on cul- tivation of microalgae under the assumption that they will excrete all the cellular TAGs that have been produced. Then, the rate of oil secretion is equal to the convertibl e lipid (CL) content in the wet lipid extraction model (2050% DWB). The media is pumped out of the PBR and the oil is then recov- ered through a conventional oil and water separator. Its cost has been evaluated between 15 and 45 /m 3 /d (30 /m 3 /d from Wright and Woods, 1993 ) with an Hydraulic Retention Time (HRT) esti- mated between 0.5 and 1.5 h and a lipid recovery efciency from 0.9 up to 0.95. The oil is then converted into biodiesel through hydrotreati ng (the same process as for HTL bio-crude upgrading). The excess biomass is harvested through the same process line as for the other models: clarier, thickener and belt lter press. It is then fermented anaerobically through a digester to produce biogas and liquid digestate. The biogas is burnt (same characteri stics than the HTL pathway for the boiler) and the digestate is recycled to the Table 1 Model parameters used for mass balances and system denition. Parameter Unit Minimum Maximum PBR/raceway ratio m 3 /m 3 0.3 0.7 CO 2 input concentration % 5 15 PBR productivity kg/m 3 day 0.65 1.95 Raceway productivity a g/m 2 day 20 30 Cultivation step HRT b day 2 6 Raceway circulation rate a m/s 0.2 0.3 Raceway depth m 0.2 0.3 Raceway evaporation rate m/year 1.8 2.4 Convertible lipid content c % 20 50 Harvesting duration h/day 1 8 Water rell duration h/day 1 8 Water recycling fraction 0.8 0.99 Clarication HRT b h 0.5 2 Biomass concentration after clarication % DWB d 1.0 2.0 Thickening HRT b H 12 48 Biomass concentration after thickening % DWB d 2.5 3.5 Biomass concentration after 1st drying step (belt lter press) % DWB d 20 30 Use of H 2 for hydrotreating kg/ton of oil e 7.5 22.5 Anaerobic digestion yield f m 3 of CH 4 /kg of algal residue 0.2 0.4 Percentage of nitrogen and phosphorus recirculated through the digestate of the anaerobic digestion g 0.3 0.6 Microalgae LHV MJ/kg 15 22 Biodiesel LHV after hydrotreating h MJ/kg 38 45 Biodiesel density after hydrotreating h kg/L 0.87 0.92 a These parameters are used by the model if raceways are considered for cultivation (HTL pathways only). b Hydraulic Retention Time. c Lipids in the harvested microalgae that can be extracted and then converted into biodiesel, estimations from microalgae lipid content and triacylglycerides (TAGs) percentage in these lipids. Parameter used in lipid excretion pathway only. d % DWB: percentage of dry weight biomass in the total medium. e Oil = either bio-crude form HTL or lipids after oil or alkane secretion. f Parameter used for pathways if anaerobic digestion is considered. Values calculated from Sialve et al. (2009). g Parameter used for pathways if anaerobic digestion is considered. Values calculated from Ras et al. (2011). h Parameters used in lipid secretion and HTL pathways. Table 2 Specic parameters for the HTL model. Parameter Minimum Maximum Unit Reference Biomass concentration 20 30 %DWB Simulations a Temperature 330 370 C Literature review b (Ross et al., 2010; Jena et al., 2011; Frank et al., 2012; Vardon et al., 2012) HRT 15 45 min Bio-crude yield 30 50 % of DWB c Solids yield 5 15 % of DWB c Solids LHV 3 9 MJ/kg Heat recycling fraction 60 85 % Simulations d Nitrogen and Phosphorus recycling fraction 10 30 % Ross et al. (2010) HTL reactor cost 1,000,000 3,000,000 /m 3 Estimations (see calculations in Supplemental material ) Heat exchanger cost 10,000 12,500 /m 2 Ross et al. (2010) a Simulations with constant biomass concentrations shows that 2030% DWB was preferable (see Supplemental material for more information). b See Supplemental material for more information. c % of DWB: percentage of the dry weight biomass converted into bio-crude/biogas. d Simulations with constant heat recycling fraction shows that a 6085% fraction was preferable (assuming a 90% efciency of the heat exchanger, see Supplemental material for more information). 208 F. Delrue et al. / Bioresource Technology 136 (2013) 205212 cultivation step to reuse the nutrients (similar to the biodiesel model, between 30% and 40% of the nitrogen and phospho rus have been assumed to be available biologica lly, Ras et al., 2011 ). 2.4.3. Alkane secretion The model for alkane secretion is very similar to the proposed model for oil secretion (Fig. 4). Alkane content has been assumed to be similar to that of oil produced (between 20% and 50% DWB). The retrieval of alkanes is performed in an oil/water separator sim- ilarly to the oil secretion model. The differences in density between the cultivatio n media and the secreted alkanes are assumed to be sufcient to allow phase separation. An additional hypothes is has been made: the alkanes secreted bythe micro-alg ae are directly use- able ina motor. It has been recently demonst rated that heterologou s expression of the alkane-synthesi zing operon of cyanobacteria in E. coli led to the production and secretion of C13C17 mixtures of al- kanes and alkenes (Schirmer et al., 2010 ). These chain lengths make this mixture of alkanes directly useable as kerosene (C10C14). Then, it is clearly conceiva ble that these secreted alkanes could be used in motors. The objective of these hypothes es is to suppress the upgrading/r ening stage in order to evaluate the potential gain in the four evaluation criteria when the secreted molecules are very close to a ready-to- use fuel. 3. Results and discussion The results of the models based on the four criteria are pre- sented in Table 3. The most inuential paramete rs deduced from the global sensitivity analyses are also discussed in this section. The full results of these analyses are available in the Supplemental material. 3.1. Importanc e of input parameters for hydrotherma l liquefaction HTL model showed similar results to the wet lipid extraction pathway (Table 3). Both pathways have great potential. Differences will be brought by the ability of the research to overcome the tech- nological barriers. Frank et al. (2012) made a Life Cycle Analysis (LCA) of biodiesel made from HTL of microalgae and compare it to the classical lipid extractio n pathway. They reported that HTL presented better bio- diesel yield but with higher greenhouse gas (GHG) emission s than through the classical lipid extractio n pathway. This work con- rmed these tendencies. First, the biodiesel yield is increased by 12% for the biodiesel yield for HTL (104,000 m 3 /y) in comparison to the wet lipid extraction pathway (91,300 m 3 /y). This increase also impacted the production cost which is reduced by the same percentage (12%) for HTL. Fig. 1. A ow chart of the major steps involved in a hydrothermal liquefaction pathway. Fig. 2. Major steps involved in biofuel production from microalgae: highlighted are the benets of oil and alkane secretion as compared to the classical pathway. F. Delrue et al. / Bioresource Technology 136 (2013) 205212 209 Then, the GHG emission s are increased by 8% on average for HTL than for the wet lipid extraction pathways. This is directly related to the higher energy demand for HTL and the reduced NER (by 9% on average). The global sensitivity analysis of the HTL pathway pointed out four important paramete rs for the energy balance: the bio-crude yield (S i,NER = 0.52) and the biodiesel Low Heating Value (LHV) (S i,NER = 0.10): the higher the bio-crude yield or the biodiesel LHV, the higher the energy output; the CO 2 rate (S i,NER = 0.11) due to the high contribution of CO 2 aeration in the energy demand (the less the CO 2 content in the aeration, the larger the required CO 2 volume and the higher the energy demand); theheat recyclingfraction(S i,NER = 0.11): underliningthenecessity of aheat exchanger betweentheinlet andoutlet of theHTLreactor. The production cost is principall y inuenced by PBR parame- ters: the PBR capital cost (S i,cost = 0.33) and the PBR productivity (S i,cost = 0.30). Similar to the wet lipid extractio n pathway, PBR rep- resents on average 75% of the total capital cost of the plant (or 58% of the production cost on average). The GHG emissions are very affected by the bio-crude yield (S i,GHG = 0.47) and moderately by the biodiesel LHV (S i,GHG = 0.04). Indeed, for constant total GHG emissions, higher energy output will decrease the GHG emission rate. Then, since the GHG emission rate of natural gas is higher than electricity, the GHG emissions are mainly inuenced by parameter related to natural gas consump - tion: heat recycling fraction (S i,GHG = 0.22) and biomass concentr a- tion for HTL (S i,GHG = 0.08). The CO 2 input concentratio n is also affecting the GHG emission rate (S i,GHG = 0.07) because it consumes high amount of electricity (41% of the cultivation step energy con- sumption on average). Fig. 3. A ow chart of the oil secretion pathway. Fig. 4. Alkane secretion pathway owsheet. 210 F. Delrue et al. / Bioresource Technology 136 (2013) 205212 The water consumptio n is driven by three types of paramete rs: (i) the water recycling fraction (S i,water = 0.23) and the cultivation HRT (S i,water = 0.10) which are directly related to water consump- tion, (ii) the parameters related to biomass or energy productivity (PBR productivity with S i,water of 0.28 and bio-crude yield with S i,water of 0.12) and (iii) the PBR/Racewa y ratio (S i,water = 0.11) since raceways are much more water-in tensive than PBR. 3.2. Residue upgrading: hydrothermal liquefaction (HTL) or anaerobic digestion (AD)? A comparison of HTL and AD for residue energy recovery has been carried out. The scenarios are based on the wet lipid extrac- tion pathway with residues upgrading either by AD or HTL. The dif- ferences are shown in Table 3. The HTL bio-crude yield has been updated in this model compared to the HTL model since HTL is per- formed on defatted residue (minimumand maximum yields of 30 40% instead of 3050% for the HTL model). Indeed, Vardon et al. (2012) noted a decrease of 9% in the bio-crude yield from 45% (for raw biomass) down to 36% for a defatted Scenedesmu s biomass. When HTL is used for residues energy recovery, the production cost is signicantly lower (average of 52.7 /GJ of biodiesel for HTL) than that needed for AD (average of 74.8 /GJ of biodiesel for AD). This difference is mainly due to the higher yield obtained with HTL (151,000 m 3 of biodiesel/y) than for AD (91,300 m 3 of biodiesel/y). A direct consequence of this higher biodiesel yield is a reduction of the water consump tion by 15% for HTL. The total energy balance is to the advantage of AD. The total energy production is higher for HTL (4.75 GWh/d of which heat represents 0.07 GWh/d) than for AD (4.19 GWh/d of which heat represents 1.36 GWh/d) but the en- ergy consump tion is reduced by 30% for AD (average of 1.97 GWh/ d for AD and 2.83 GW/d for HTL). Similarly, the GHG emission rate is roughly 28% higher for HTL because of the high heat demand. Finally, the main advantag e of residues upgrading by HTL over AD is its ability to increase the biodiesel yield signicantly. 3.3. Advantages of oil secretion The results of the oil secretion pathway for the four evaluation criteria are summarized in Table 3. Compared to the wet lipid extraction pathway, the NER is increased by 35% on average and the impacts on the environm ent (GHG emission s and water con- sumption) are much lower. However, the production cost is in- creased by more than 10% since only PBR can be used for the cultivation step (69% of the total capital cost on average and the capital cost allowance, directly related to the capital cost, is responsib le for 88% of the production cost on average). The oil secretion pathway is dependent on the developmen t of new low- cost design of PBR. In this study, the oil secretion pathway has been associate d with AD. A wet conversion process of the residues (AD like in these simulatio ns or possibly HTL) is indeed interesting or even neces- sary. Otherwise, the NER would decrease from 2.95 to 2.09 on aver- age. Similarly , the GHG emission rate would increase from 13.7 to 20.2 kgCO 2 -eq/GJ and the water consumptio n from 3800 to 5610 L of water/GJ (scenarios averages). The global sensitivity analysis showed that the oil secretion rate is, by far, the most important factor (S i,NER = 0.53, S i,cost = 0.44, S i,GHG = 0.42 and S i,water = 0.19). The CO 2 input concentration is a paramete r with an high inuence on the energy balance and there- fore on the GHG emissions (S i,NER = 0.28 and S i,GHG = 0.10). The pro- duction cost is also driven by the PBR parameters: PBR capital cost (S i,cost = 0.22) and the PBR productivi ty (S i,cost = 0.13). Other param- eters than the oil secretion rate are inuencing the water con- sumption: the PBR productivity (S i,water = 0.36), the water recycling fraction (S i,water = 0.16) and the HRT (S i,water = 0.12). 3.4. Additiona l advantages provided by secretion of directly useable alkanes Alkane secretion signicantly improved the energetic balance (Table 3). The NER is increased by 24% on average compared to that of wet lipid extraction pathway. The production cost and the GHG emission rate are slightly reduced (4% and 8%, respectively). How- ever, the improvements are not signicant. The PBR capital cost and the rate of alkane secretion are inuencing the production cost much more than the HDO paramete rs. Similarly, the high impact of rate of alkane secretion on the GHG emission rate reduces the im- pact of not needing rening for alkane secretion . The results of the global sensitivit y analyses for oil or alkane secretion s are identical except for the HDO parameters inuencing the NER (hydrogen use for HDO with S i,NER = 0.097 and HDO heat consump tion with S i,NER = 0.032 for oil secretion). 4. Perspective s To further improve the actual techno-economi c model, a specic model for hydro-treatm ent would certainly benet tothe evaluation of the H 2 consumptio nand the energy demand of this step. This sim- ulation will require mass balances at the elemental level on the whole process. However , this level of details will only be needed when experimental data are available at a larger scale especially in Table 3 Modelling results for the three pathways in comparison to petroleum diesel. Pathway NER (GJ produced/GJ consumed) Production cost (/GJ of biofuel) GHG emission rate (kgCO 2 /GJ produced) Water consumption (L of water/GJ produced) Y 25% Y 75% Mean value Y 25% Y 75% Mean value Y 25% Y 75% Mean value Y 25% Y 75% Mean value Petroleum diesel 4.90 a 16.2 b 69.4 c 360 d Biodiesel from wet lipid extraction e 1.85 2.46 2.18 52.1 90.9 74.8 18.5 26.0 22.5 4240 6910 5860 Biodiesel from HTL 1.75 2.22 1.99 50.0 77.7 65.9 20.9 27.1 24.3 5130 8500 7170 Biodiesel from wet lipid extraction + HTL of residues 1.43 1.86 1.66 41.8 61.1 52.7 24.0 33.1 28.9 3620 5890 4990 Biodiesel from oil secretion 2.61 3.28 2.95 58.2 103.0 84.1 11.9 15.2 13.7 2800 4500 3800 Direct-useable fuel from alkane secretion 3.09 4.18 3.65 55.5 99.6 81.0 10.6 14.2 12.6 2790 4480 3790 a Cherubini et al. (2009). b EIA (2011). c LHV petroleum diesel = 35.8 MJ/L (MIT Energy Club FactSheet available at http://www.mitenergyclub.org/assets/2008/11/15/ Units_ConvFactors.MIT_EnergyClub_Factsheet.v8.pdf). d King and Webber (2008). e From Delrue et al. (2012). F. Delrue et al. / Bioresource Technology 136 (2013) 205212 211 a continuous operation. Indeed, it is likely that the bio-crude ele- mental analysis as well as the HRT or the impact of the operating conditions would change when operating in a continuous mode. This study does not consider non-energe tic products such as feed, food, nutraceuticals, pharmac euticals or chemical precursor s. The road to make biofuel affordable will denitely be associate d with these co-products (Brennan and Owende, 2010 ). A next step would be to integrate them into the model in order to evaluate their potential for reducing biofuel production cost. However, the process line has to be thoroughly designed since the size of the market for most of these co-products is hardly compatib le with those of liquid fuel (90 million barrels per day in 2012, from EIA, the U.S. Energy Information Administrati on). In this context, the process reported by Chakraborty et al. (2012) is of interest as it is based on sequential HTL that can re- cover simultaneously bio-crude and polysacchari des. Finally, assumpti on has been made that all the technologic al as well as biological barriers have been overcome for the selected pathways. Thus, the results have to be put into the perspecti ve that the models do not take into account the scientic challenges that still exist. The technologies that will emerge will not necessarily be the technology with the best potential but the one with the most important technological breakthr ough. More detailed analy- ses on a larger scale are needed to decrease the level of uncertain- ties and improve the models. 5. 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