Applied Energy 101 (2013) 226236

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Applied Energy
journal homepage: www.elsevier.com/locate/apenergy

Evaluation of alternatives for microalgae oil extraction based on exergy analysis

Y. Peralta-Ruiz, A.-D. Gonzlez-Delgado, V. Kafarov
Research Center for Sustainable Development in Industry and Energy, Department of Chemical Engineering, Industrial University of Santander, Colombia

h i g h l i g h t s

" Exergy analysis was used as decision-making tool for evaluation of microalgae oil extraction.
" A robust composition of Chlorella sp. biomass was modeled and used for simulation.
" Three solvent-based microalgae oil extraction methods at large scale were compared.
" Hexane based extraction presented the highest exergetic efciency.

a r t i c l e i n f o a b s t r a c t

Article history: Several technologies for microalgae oil extraction are being evaluated in order to nd the most adequate
Received 10 December 2011 for large scale microalgae processing. In this work, exergy analysis was used as an instrument for screen-
Received in revised form 19 June 2012 ing three design alternatives for microalgae oil extraction in a large-scale process and as a decision-
Accepted 29 June 2012
making tool for evaluation and selection of novel technologies from the energy point of view. Routes were
Available online 24 August 2012
simulated using dedicated industrial process simulation software, taking as feedstock a representative
and robust modeled composition of Chlorella sp. microalgae biomass. Mass, energy and exergy balances
Keywords:
were performed for each alternative, and physical and chemical exergies of streams and all specic mic-
Microalgae biomass
Exergy analysis
roalgae constituents modeled were calculated with the help of the thermodynamic properties of biomass
Oil extraction components and operating conditions of streams.
Third generation biofuels Exergetic efciencies, total process irreversibilities, energy consumption and exergy destruction were
calculated for all solvent-based microalgae oil extraction pathways evaluated. It was shown that exergy
analysis led to identify the hexane-based oil extraction (HBE) as the most adequate alternative of the
routes assessed for scaling up from the energy point of view, presenting a maximum exergy efciency
of 51% and exergetic losses of 982,000 MJ considering a production of 104,000 t of microalgae oil per year.
2012 Elsevier Ltd. All rights reserved.

1. Introduction biosynthesize and accumulate large amounts of lipids and/or sug-

Nowadays, the continued use of fossil-derived fuels is recog-
nized as unsustainable due to the exhaustion of supplies and their
contribution to environmental pollution. This kind of fuels has to
be replaced with clean and renewable energy. In response to this
issue, environmental policies worldwide have favored the increase
in research, development and the use of biofuels, mainly those that
can replace fossil fuels used in transportation. Biofuels offer many
benets associated with energy security, economic stability and
reduction of the environmental impact of greenhouse gases [1].
Third-generation biofuels are derived from microorganisms,
such as yeast, fungi and microalgae, some of these microbes can
Corresponding author. Address: Research Center for Sustainable Development
in Industry and Energy, Department of Chemical Engineering, Industrial University
of Santander, K 27 Cll 9 Bucaramanga, Colombia. Tel.: +57 7 6344000x2603.
E-mail address: Kafarov@uis.edu.co (V. Kafarov).
ars [2], fungi like Trichosporon fermentans have been studied for
microbial oil production and biodiesel preparation [3,4], however,
the most attractive source for third generation biofuels production
are microalgae. They have recently been rediscovered as promising
candidates for biotechnological applications and efcient energy
production systems [5]. Depending on the strain, microalgae can
grow in a wide range of temperatures, pH and nutrients availabil-
ity. They have a growth rate between 20 and 30 times higher than
other sources for biofuels, some microalgae species have the ability
to produce up to 20 times more oil per unit area than palm [6], oil
content of certain strains in some cases exceeds 80% in dry weight
biomass under appropriate conditions [7]. Microalgae can grow in
warm, tropical, and subtropical climates, for biomass production it
only requires water, some nutrients, a carbon source and a high
and constant sun irradiance. Microalgae can be cultivated in pho-
tobioreactors which offer high biomass productivities and an
adaptable illumination, open ponds which can be natural systems

0306-2619/$ - see front matter 2012 Elsevier Ltd. All rights reserved.
http://dx.doi.org/10.1016/j.apenergy.2012.06.065
 Y. Peralta-Ruiz et al. / Applied Energy 101 (2013) 226236
(e.g. lagoons and lakes) or articial systems (e.g. stirred tanks and
raceway ponds) which require low energy consumption and are
easy to maintain. This condition makes feasible the use of non-
arable lands for photobioreactor assembly or open pond building.
Microalgae can also be cultivated using as culture media waste
water or sea water. Due to its high growth rate, microalgae bio-
mass can be harvested 365 days per year. Taking into account
the issues mentioned above, microalgae presents a theoretical po-
tential to become a viable alternative to replace petroleum-based
liquid fuels in the future without the disadvantages associated
with food vs. fuel discussion and use of land, showing a prospective
of a continuous biofuel production chain as occurs in traditional oil
reneries. However, to make this possible, it is important to im-
prove technical, environmental and economic aspects such as
water requirements, production costs, environmental impacts
and process efciency, among others [1].
However, biodiesel-from-microalgae production chain is still
away from sustainability by several factors, in energy terms, Khoo
et al. [8], presented a comparison of energy and environmental
performance of biodiesel from microalgae case studies previously
developed by several authors referenced in the paper, with two
additional cases proposed by the authors mentioned, using the
methodology of Life Cycle Assessment (LCA) including energy
and CO2 balance, in which, for all systems analyzed, the compari-
son of life cycle energy demands in MJ per MJ of biodiesel are po-
sitive, even if energy requirements of lipid extraction and biodiesel
production are not included as occurs in two of compared cases.
Total energy inputs for the system proposed by authors were cal-
culated in 85% for lipid extraction, 13% for biomass production
and 2% for transesterication, concluding that main bottleneck
lie in high energy requirements for lipid extraction and pointing
out this issue as a main challenge to overcome in order to make
biodiesel from microalgae production chain feasible and practical.
These results show the necessity of future studies related to micro-
algae lipid extraction in order to improve this process in terms of
efciency, purity of product, energy requirements, costs and envi-
ronmental impacts.
Studies about microalgae oil extraction for biodiesel production
are taking signicance because the efciency of biodiesel produc-
tion chain from microalgae depends in a great way on the oil
extraction efciency. There are several oil extraction methods
which have been used on microalgae, these methods can be di-
vided in:
 Methods assisted by mechanical disruption which uses cell
homogenizers, ball mills, pressing systems, among others;
these methods are not suitable for a lab-scale oil extraction
because presents high biomass losses and low selectivity to
lipids.
 Enzyme-assisted extraction methods, where microalgae cell
wall is degraded by enzymes allowing lipids release, how-
ever, enzymatic activity is affected by several variables
including concentration and ratio of system compounds,
fatty acid prole, microalgae composition, temperature,
among others. These issues make this route hard to main-
tain in this moment for a large scale biomass processing.
Other methods evaluated on microalgae are ultrasound-assisted
extraction, microwave-assisted extraction, supercritical uid
extraction, autoclave and solvent based extractions [9].
A wide variety of organic solvents are often used to extract oil
from microalgae, where hexane and ethanol are the most popular.
However, ethanol is a polar solvent and its selectivity to lipids is
relatively low compared to other solvents, so in extractions with
ethanol, other microalgae components may also appear, such as
sugars, pigments or aminoacids. Using a mixture hexane-ethanol,
227
around of 80% of fatty acids presents into biomass can be extracted
[10]. Solvent based lipid extraction methods as Folch, and Bligh
and Dyers method which uses a methanolchloroform mixture
have been tested successfully in oil extraction from microalgae
[11], although this method is not very environmentally friendly
due to the toxicity of the solvents used. Ethers present the disad-
vantage of high volatility, this increase solvent losses at long
extraction times. Hexane is frequently used for soxhlet extraction
using microalgae biomass as raw material [12], hexane is cheaper
than other non-polar solvents like cyclohexane, which is easy to re-
cover after extraction and it is selective to neutral lipids. In addi-
tion, it can be used in mixture with isopropanol [13], which is
considered safe in an industrial scale and is used for lipid extrac-
tion from soybean.
2. Exergy analysis
Thermodynamic techniques like energy analysis, exergy analy-
sis, emergy analysis, among others have been widely used for eval-
uation of industrial systems and thermal energy storage processes
[1417]. Energy analysis includes balances based on the rst law of
thermodynamics, and calculation of energy efciencies for the
steps studied. However, an energy balance neither offers informa-
tion related with the energy degradation nor quanties the useful-
ness or quality of the mass and energy streams of the system
evaluated. Exergy analysis is presented as an alternative which
overcomes the limitations of the rst law of thermodynamics.
Exergy analysis shows the sites of energy degradation in a process
and can help to improve a unitary operation, a technology or a pro-
cess [18]. In addition, exergy analysis allows to evaluate and select
different alternatives to improve the design of a process, which
makes it an appropriate tool for evaluation of novel technologies
for advanced biofuels production.
The term exergy can be dened as the maximum theoretical
useful work that could be obtained from a system that interacts
only with the environment if this has not reached the thermody-
namic equilibrium [19], taking into account that, the exergy of a
system depends on the reference state selected, for this reason, a
good choice of reference state must be made in order to avoid erro-
neous results.
For a general steady state, steady-ow process, four balance
equations must be applied in order to nd the work and heat inter-
actions. These equations are the principle of mass/matter conser-
vation given by Eq. (1), the rst law of thermodynamics given by
Eq. (2), the second law of thermodynamics given by Eq. (3), and
the global exergy balance given by Eq. (4).
_ i in Ri m
Ri m _ i out 1
Ri m _ i  hi out Q_  W
_ i  hi in Ri m _ 0 2
Q_ i _
_ i  si in Ri m
Ri m _ i  si out Ri Sgeni 3
Ti
_ mass;in  Ex
_ mass;out Ex
_ heat  Ex
_ work Ex
_ loss
Ex 4
Mass exergy component expressed as is shown in Eq. (5), is di-
vided into four specic components: the physical exergy (Exphy) re-
lated to temperature, enthalpy and entropy given by Eq. (6);
chemical exergy (Exchem) related to the chemical exergy of each
compound per mol (Exoch ); potential exergy, Expot and kinetic exer-
gy, Exkin. The calculation of the chemical exergy of each compound
per mol (Exoch ) is given by Eq. (7), and is a function of the chemical
exergy of each elemental compound (Exoch;elem ), the number of
atoms of each element contained into the stream (nelem) and the
Gibbs free energy of formation for the compound (DGof ) [20]. The
228 Y. Peralta-Ruiz et al. / Applied Energy 101 (2013) 226236
chemical exergy of the process streams was evaluated by Eq. (8),
where yi is the molar fraction of the component i, Exoch;i is chemical
exergy of pure compound, To is reference temperature and R is the
gas constant. Kinetic and potential exergy was neglected because
its contribution to the total exergy balance is minimal. Regarding
exergy balance, the exergy transfer by heat ow at a temperature
T (Exheat) and exergy by work ow (Exwork) was evaluated by Eqs.
(9) and (10) respectively [18].
_ mass Ex
Ex _ phy Ex
_ chem Ex
_ pot Ex
_ kin
_ phy H_  H_ o  T o  S_  S_ o
Ex
Exoch DGof Ri nelem  Exoch;i
Exch;mx Ri yi  Exoch;i RT o Ri yi  lnY i 8 oped by Sanchez et al. [28], a robust model of microalgae oil was
 
To
_ heat
Ex 1  Q_
T
_ Work W
_ strain and taking into account that in transesterication stage,
Ex
Exergy analysis can be used as a decision-making tool for select-
ing and improving technologies from the energy point of view. This
analysis has been recently used to study existing and emerging
technologies proposed for biofuels production chains from several
feedstocks [2123] including microalgae [22,23]. Peralta et al. [22],
studied microalgae oil transesterication using four fatty acids and
four triglycerides for modeling microalgae oil composition nding
an exergy efciency of 79% for this stage. Ofori-Boateng et al. [23],
used exergy analysis to study the feasibility of microalgal and
jatropha biodiesel production plants using three triglycerides as
representative microalgae oil, performing extraction with metha-
nol at temperatures between 333 and 338 K by the use of a li-
quidliquid extraction tower, and concludes that oil extraction
units showed the highest exergy loses, however, microalgae oil
extraction stage is not deeply studied in this reference. Is clear that
exergy analysis of microalgae oil extraction stage focused the eval-
uation and comparison of different solvent-based techniques using
a robust model of a microalgae strain which includes carbohy-
drates, proteins, aminoacids and a detailed fatty acid prole has
not been developed until now.
In this work, three solvent-based microalgae oil extraction
methods were evaluated using exergy analysis as an instrument
for screening design alternatives for scaling up and as a decision-
making tool for evaluation and selection of novel technologies
from the energy point of view, exergetic efciency of the routes, to-
tal irreversibilities, energy utilities required and exergy destruction
were calculated for each oil extraction method. Through this re-
search, four contributions to the microalgal biotechnology research
were made:
 Development of a robust model of microalgae Chlorella sp.
biomass composition, for use in process simulation, based
on experimental strain characterization reported, which
includes proteins, aminoacids, carbohydrates, triglycerides
and fatty acids.
 The simulation in large scale of three detailed solvent-based
microalgae oil extraction methods: hexane based extraction
(HBE), oil extraction using the mixture ethanol/hexane (EHE)
and extraction with methanolchloroform mixture (SHE).
 The calculation of chemical exergies for all specic microal-
gae constituents used for simulation.
 The evaluation based on exergy analysis of simulated micro-
algae oil extraction methods and selection of the best
method from the energy point of view.
3. Materials and methods
In this study, microalgae Chlorella sp. was used as the represen-
tative genera, because this strain present high growth rates and
can produce large quantities of lipids [24]. For the simulation of
microalgae Chlorella sp. biomass composition, normalization was
made taking into account experimental information reported in lit-
erature and unpublished results obtained in lab-scale by authors.
Oil content of microalgae strain was xed in 30% [25], which cor-
5 responds to 5.11% of free fatty acids and 94.89% corresponding to
triglycerides [26], the same percentage distribution was taken for
6 fatty acids present in triglyceride prole, based on the work asso-
ciated to Chlorella sp. microalgae oil composition developed by Pet-
7 kov and Garcia [27], and the simulation of Chlorella vulgaris
microalgae oil for a esterication/transesterication process devel-
developed, containing 9 fatty acids and 9 triglycerides, protein per-
centage was xed in 40%, as assumption, triglycerides present in
9 microalgae oil were considered homogeneous by a lack of a repre-
sentative triglyceride prole reported in literature for Chlorella sp.
10
these chains are broken for biodiesel production obtaining a
known fatty acids methyl esters prole [29], aminoacids present
in signicant percentage were also simulated [30], carbohydrates
percentage was xed in 25% divided in lignin, cellulose and hemi-
cellulose [31].
3.1. Process simulation
The development of process simulation mainly involve select-
ing chemical components used in the process, choosing an appro-
priate thermodynamic model, determining plant capacity, using
suitable operating units and setting up input conditions such as
ow rate, temperature, pressure, among others [32]. For the simu-
lation of oil extraction alternatives was used the industrial process
software Aspen Plus, version 7.1, which has been widely used for
studies related to simulation of existing and emerging technologies
for biofuels and co-products production in large scale using several
feedstocks [3335], chemical compounds available in the software
database were selected and used, for compounds without availabil-
ity in the software library, molecules were created using Symyx
Draw, and exported to Aspen Plus 7.1 using the User Dened
Compound Wizard tool, also some properties known as normal
boiling point, molecular weight, acentric factor and critical proper-
ties were introduced. Unknown properties were estimated using
UNIFAC (Universal Functional Group Activity Coefcient) model
and the database Thermo Data Engine (TDE). Thermodynamic
properties were calculated based on molecular structures of each
compound, NRTL (Non-Random Two Liquids) thermodynamic
model was used for extraction routes simulation, this model was
chosen because of its good representativeness of polar-non polar
mixtures. Binary interaction coefcients were calculated by the
UNIFAC method.
Oil production capacity was chosen taking into account the nec-
essary oil amount to produce 100,000 t/year of third generation
biodiesel, which corresponds to an approximate lipid ow of
104,000 t/year. The main processing units for the three oil extrac-
tion routes include distillation columns, heat exchangers, pumps,
mixers, liquidliquid and solidliquid separators. Mixers were
used for blending solvents with biomass. Heaters were utilized
for heating and cooling streams and centrifugal pumps were used
for moving liquid streams. Separation of liquid phases was carried
out using decanters. Separation and recovery of solvents in all
methods were made by the use of distillation towers with ten ideal
stages with total condenser and kettle reboiler in order to recover
around 95% of the solvents in the oil stream.
 Y. Peralta-Ruiz et al. / Applied Energy 101 (2013) 226236 229

In order to avoid difculties presented in lab scale related to
purity of oil extracted given by selectivity of solvents which are
pointed out in Section 1. In the stage of lipid separation hydrocyc-
lons and lters were used for homogenization and separation of
the microalgae solids from the oil. Continuous rotary vacuum l-
ters were also included with the objective of removing most of
the remaining solids, obtaining a separation efciency of 97%. For
the simulation of all routes, an oil extraction efciency of 98%
was assumed in order to obtain the maximum exergetic efciency
which is possible to reach.
Solvent-based oil extraction methods included in this study
where previously adjusted in lab-scale in order to obtain the best
operating conditions for simulation. The routes selected were hex-
ane-based extraction (HBE), oil extraction using the mixture etha-
nol/hexane (EHE) and extraction with methanolchloroform
mixture (SHE). The rst one is a batch microalgae oil extraction
method and was reported by Garca et al. [36].
To perform this method, hexane is added to microalgae biomass
under environmental conditions (298 K, 101.325 kPa) in a 20:1
mass ratio, after that, mixture is separated and ltered, obtaining
a liquid stream rich in hexane and oil, and a stream of biomass rich
in carbohydrates and proteins. Oil/hexane stream is separated
through distillation and hexane is recirculated to the process, li-
quid components present in biomass stream after ltration are

Fig. 1. Schematic ow sheet of oil extraction methods evaluated using exergy analysis.
230 Y. Peralta-Ruiz et al. / Applied Energy 101 (2013) 226236

separated and puried in order to increase extraction efciency, Table 1

this method was chosen due to its easiness to perform and similar- Modeled composition of Chlorella sp. microalgae.

ity with solvent-based processes for oil recovery from soybean. Components Chlorella sp. composition (%)
The second route is based on a modication of a lipid extraction Free fatty acids
method developed by Fajardo et al. [10], and adapted to local con- C14:00 0.14
ditions and feedstocks [37]. As a rst step, crude microalgae oil was C16:00 0.38
extracted by mixing ethanol with biomass in a mass ratio 4:1 at C16:01 0.03
C16:02 0.15
environmental conditions (298 K, 101.325 kPa), the mixture is stir- C16:03 0.14
red and goes to a separation process using a hydrocyclone in which C18:00 0.01
solid and liquid phases are separated, residual biomass is once C18:01 0.08
again sent to be mixed with ethanol in order to increase process C18:02 0.31
C18:03 0.29
efciency, liquid water is added until an ethanol concentration of
Total free fatty acids 1.53
40% is reached and hexane is also added in a 1:1 ratio with hydro-
Triglycerides
alcoholic solution.
TAG-C14:00 2.56
The mixture is placed in a decanter where hydrophilic/hydro- TAG-C16:00 7.15
phobic phases are separated, hexane phase with selected lipids is TAG-C16:01 0.57
distilled obtaining a product stream, hexane is recirculated and TAG-C16:02 2.85
hydroalcoholic phase is also distillated recovering part of the eth- TAG-C16:03 2.56
TAG-C18:00 0.26
anol for reuse in the process.
TAG-C18:01 1.42
The last route evaluated was developed at lab-scale as a modi- TAG-C18:02 5.69
cation of the method of Bligh and Dyer for microalgae biomass TAG-C18:03 5.41
with high percent of ash [38]. Methanol, chloroform and biomass Total triglycerides 28.47
are mixed under environmental conditions in a mass ratio of Amino acids
6:12:1, the mixture is homogenized and separated by ltration, Aspartic acid 4.49
Glutamic acid 5.47
obtaining a liquid stream with high percentage of lipids and a solid
Glycine 4.35
stream of biomass, the former is mixed with water in 4:1 ratio for Alanine 5.40
phase separation. Valine 3.86
The hydrophilic/hydrophobic phases are separated and each Leucine 4.28
stream is distillated in order to obtain algae oil, methanol, chloro- Proline 5.05
Lysine 7.15
form and wastewater. Solvents are recycled in order to decrease
Total amino acids 40.05
environmental impacts related to photochemical oxidation, acidi-
Carbohydrates
cation, eutrophication and fossil energy consumption. Although
Cellulose 7.10
this method uses highly toxic solvents, it was included due to its Lignin 1.52
high efciency of total lipids extraction in comparison to other Hemicellulose 16.30
methods in lab scale and the need of its evaluation from the energy Total carbohydrates 24.92
point of view. Fig. 1 shows the schematic owsheet of oil extrac- Water 5.03
tion methods evaluated. Total microalgae 100.00
Estimation of energy consumption for each oil extraction meth-
od was made based on requirements of thermal energy for heat
exchangers, reboilers and related operation units, obtained from
of other biofuels and high value products by the presence of essen-
each simulation performed. Global mass balance of all currents of
tial aminoacids a lysine and their low lignin percentage.
the process was performed, and the thermodynamic properties
needed to develop the exergy balance were obtained as described
in the beginning of this section. After that, chemical and physical 4.1. Simulation of three solvent-based microalgae oil extraction
exergies of streams involved in the routes were calculated. Each methods
unit operation was independently balanced. Exergy was deter-
mined for each compound, mixture and utilities. As dead state con- According to simulation of microalgae oil extraction methods
ditions were taken environmental conditions (298 K, 101.325 kPa), four general stages are common in all methods: biomass-solvent
exergetic efciency of each oil extraction method was calculated mixing, oil extraction, solvent recovery (oil separation) and solids
using the following equation. drying, simulation of hexane-based extraction route (HBE) is
  shown in Fig. 2. The system with four mixing units for fresh solvent
Exergy loss input, solvent biomass mixing post-extraction solids mixing and li-
w1 11
Exergy input quid oil/hexane streams combination have to be incorporated. Sol-
ids streams after oil extraction are rich in carbohydrates and
proteins as shown in Table 2, composition of this stream conrms
4. Results and discussion the potential of coproduct as a feedstock for downstream process-
ing, stream 101 which corresponds to microalgae oil extracted,
As shown in Table 1, composition of microalgae biomass is presents a free fatty acid mole fraction of 0.14 which shows that
more complex than previous studies where microalgae oil is com- lipids obtained can be used for a transesterication process with-
posed only by triolein or all microalgae biomass is simulated as a out the need of previous free fatty acids esterication.
unique hypothetical component. Saturated and unsaturated tri- Results of ethanolhexane route (EHE) simulation (Fig. 3), show
glycerides were taken into account corresponding to 18.5% and that more steps are needed for a continuous extraction process, as
9.97% of total biomass composition respectively, a more realistic occurs in lab-scale; this means the installation of more equipment
composition supposes more trustable simulation and exergy anal- affecting the technical practicability of the route and the economy
ysis results. Complete biomass composition collected shows the of the process. However the use of ethanol gives the possibility of
potential of this feedstock for a complete use in the production several operation alternatives in a complete production chain, for
 Y. Peralta-Ruiz et al. / Applied Energy 101 (2013) 226236 231

Fig. 2. Simulation of hexane method for microalgae oil extraction (HBE).

Table 2
Main process streams conditions for hexane based microalgae oil extraction (HBE).

Streams 101 106 109 111 112 114 116 117 118
Pressure (kPa) 101.325 101.325 101.325 101.325 101.325 70.927 101.325 70.927 101.325
Temperature (K) 554.8 298 298 298 298 298 298 298 433
Mass ow (kg/h) 12236.44 726857 36669 746488.20 745839 44461.65 43451.43 1010.22 23820.18
Component (mole fraction)
Cellulose 0 0 0.06 0 0 0.04 0.04 0.05 0.08
Lignin 0 0 0.01 0 0 0.01 0.01 0.01 0.02
Hemicellulose 0 0 0.17 0 0 0.1 0.1 0.14 0.21
Aspartic 0 0 0.05 0 0 0.03 0.03 0.04 0.06
Glutamic 0 0 0.05 0 0 0.03 0.03 0.04 0.06
Glycine 0 0 0.1 0 0 0.06 0.06 0.08 0.13
Alanine 0 0 0.1 0 0 0.06 0.06 0.08 0.13
Valine 0 0 0.05 0 0 0.03 0.03 0.04 0.07
Leucine 0 0 0.05 0 0 0.03 0.03 0.04 0.06
Proline 0 0 0.07 0 0 0.04 0.04 0.06 0.09
Lysine 0 0 0.08 0 0 0.04 0.04 0.06 0.1
C14H2-01 0.01 0 0 0 0 0 0 0 0
C16H3-01 0.04 0 0 0 0 0 0 0 0
C16H3-02 0 0 0 0 0 0 0 0 0
C16H3-03 0.01 0 0 0 0 0 0 0 0
C16H3-04 0.01 0 0 0 0 0 0 0 0
C18H3-01 0 0 0 0 0 0 0 0 0
C18H3-02 0.01 0 0 0 0 0 0 0 0
C18H3-03 0.03 0 0 0 0 0 0 0 0
C18H3-04 0.03 0 0 0 0 0 0 0 0
TGC14-01 0.09 0 0.01 0 0 0 0 0 0
TGC16-01 0.21 0 0.01 0 0 0 0 0 0
TGC16-02 0.02 0 0 0 0 0 0 0 0
TGC16-03 0.09 0 0.01 0 0 0 0 0 0
TGC16-04 0.08 0 0.01 0 0 0 0 0 0
TGC18-01 0.01 0 0 0 0 0 0 0 0
TGC18-02 0.04 0 0 0 0 0 0 0 0
TGC18-03 0.16 0 0.01 0 0 0 0 0 0
TGC18-04 0.15 0 0.01 0 0 0 0 0 0
H2O 0 0.01 0.14 0.01 0 0 0 0 0
C6H14 0.03 0.99 0 0.99 1 0.52 0.53 0.37 0

example, the use of stream 112 which corresponds to ethanol out-
put at 350 K from DESTL-2 can be used in transesterication stage
for ethylesters production. As shown in Table 3, an effective lipid
separation was reached and mass ow distribution in route stages
is different to mass ow in HBE route, caused by the presence of
additional steps.
The simulation of solvent-based oil extraction with homogeni-
zation using the mixture methanolchloroform (SHE), involves
the use of two solvents, these are added in the same process unit
(MIX-1), for this reason, only one hydrocyclone is necessary for
oil separation as is shown in Fig. 4. Route needs less equipment
in comparison to EHE route, but two separation units are also need
for chloroform-lipids and methanolwater mixtures. Table 4
shows the main process streams conditions for SHE route, differ-
ences in temperatures of streams are caused by the nature of sol-
vents used in this route.
4.2. Exergy analysis of microalgae oil extraction methods
The process of extracting oil from microalgae for all routes can
be divided into four general steps: biomass-solvent mixing, oil
extraction, solids drying and solvent recovery. Taking into account
232 Y. Peralta-Ruiz et al. / Applied Energy 101 (2013) 226236

Fig. 3. Simulation of microalgae oil extraction using the mixture ethanolhexane (EHE).

Table 3
Main process streams conditions for microalgae oil extraction using the mixture ethanolhexane (EHE).

Streams 115 118 119 122 124 125 128 129 130 132
Pressure (kPa) 101.325 101.325 101.325 101.325 101.325 101.325 101.325 101.325 101.325 51.67
Temperature (K) 302 604.6 297.7 298 297.7 297.9 302.2 297.7 297.9 297.9
Mass ow (kg/h) 653366.7 12212.38 177640.3 36662 210744.3 128752.5 1286204 33104.07 28405.48 31675.21
Component (mole fraction)
Cellulose 0 0 0 0.06 0 0.01 0 0.04 0.03 0.04
Lignin 0 0 0 0.01 0 0 0 0.01 0.01 0.01
Hemicellulose 0 0 0 0.17 0.01 0.02 0 0.1 0.09 0.11
Aspartic 0 0 0 0.05 0 0 0 0.03 0.02 0.03
Glutamic 0 0 0 0.05 0 0 0 0.03 0.03 0.03
Glycine 0 0 0 0.1 0.01 0.01 0 0.06 0.05 0.07
Alanine 0 0 0 0.1 0.01 0.01 0 0.06 0.05 0.07
Valine 0 0 0 0.05 0 0 0 0.03 0.03 0.04
Leucine 0 0 0 0.05 0 0 0 0.03 0.03 0.03
Proline 0 0 0 0.07 0 0.01 0 0.04 0.04 0.05
Lysine 0 0 0 0.08 0 0.01 0 0.04 0.04 0.05
C14H2-01 0 0.01 0 0 0 0 0 0 0 0
C16H3-01 0 0.04 0 0 0 0 0 0 0 0
C16H3-02 0 0 0 0 0 0 0 0 0 0
C16H3-03 0 0.02 0 0 0 0 0 0 0 0
C16H3-04 0 0.01 0 0 0 0 0 0 0 0
C18H3-01 0 0 0 0 0 0 0 0 0 0
C18H3-02 0 0.01 0 0 0 0 0 0 0 0
C18H3-03 0 0.03 0 0 0 0 0 0 0 0
C18H3-04 0 0.03 0 0 0 0 0 0 0 0
TGC14-01 0 0.09 0 0.01 0 0 0 0 0 0
TGC16-01 0 0.22 0 0.01 0 0 0 0 0 0
TGC16-02 0 0.02 0 0 0 0 0 0 0 0
TGC16-03 0 0.09 0 0.01 0 0 0 0 0 0
TGC16-04 0 0.08 0 0.01 0 0 0 0 0 0
TGC18-01 0 0.01 0 0 0 0 0 0 0 0
TGC18-02 0 0.04 0 0 0 0 0 0 0 0
TGC18-03 0 0.16 0 0.01 0 0 0 0 0 0
TGC18-04 0 0.15 0 0.01 0 0 0 0 0 0
H2O 0 0 0.15 0.14 0.14 0.12 0.62 0.08 0.08 0.06
C6H14 0.97 0.01 0 0 0 0 0.21 0 0 0
C2H6OH 0.03 0 0.84 0 0.81 0.8 0.17 0.45 0.5 0.4

simulation results and composition for each stream; physical and
chemical exergies were estimated, Table 5 shows chemical exer-
gies calculated for the main components of microalgae oil extrac-
tion, values calculated for known components as water or
ethanol were validated with values reported in literature, highest
specic chemical exergies corresponds to triglycerides which are
the product of interest for further biodiesel production. Exergy of
heat ux was also considered and calculated. Table 6 shows power
consumption of equipments in the three routes of extraction
including hydrocyclons, lters and pumps, as shown, highest en-
 Y. Peralta-Ruiz et al. / Applied Energy 101 (2013) 226236 233

Fig. 4. Simulation of microalgae oil extraction using the mixture methanolchloroform (SHE).

Table 4
Main process streams conditions for microalgae oil extraction using the mixture methanolchloroform (SHE).

109 110 111 113 114 118 120 123 124

Pressure (kPa) 101.325 101.325 101.325 101.325 101.325 101.325 101.325 51.67 101.325
Temperature (K) 299 586.8 296.6 296.6 298 296.6 299.1 296.6 427.7
Mass ow (kg/h) 447383.7 12212.6 651982.8 651298.4 36687 691686.7 810963.3 40388.27 23831.88
Component (mole fraction)
Cellulose 0 0 0 0 0.06 0 0 0.03 0.08
Lignin 0 0 0 0 0.01 0 0 0.01 0.02
Hemicellulose 0 0 0 0 0.17 0 0 0.1 0.21
Aspartic 0 0 0 0 0.05 0 0 0.03 0.06
Glutamic 0 0 0 0 0.05 0 0 0.03 0.06
Glycine 0 0 0 0 0.1 0 0 0.06 0.13
Alanine 0 0 0 0 0.1 0 0 0.06 0.13
Valine 0 0 0 0 0.05 0 0 0.03 0.07
Leucine 0 0 0 0 0.05 0 0 0.03 0.06
Proline 0 0 0 0 0.07 0 0 0.04 0.09
Lysine 0 0 0 0 0.08 0 0 0.04 0.1
C14H2-01 0 0.01 0 0 0 0 0 0 0
C16H3-01 0 0.04 0 0 0 0 0 0 0
C16H3-02 0 0 0 0 0 0 0 0 0
C16H3-03 0 0.02 0 0 0 0 0 0 0
C16H3-04 0 0.01 0 0 0 0 0 0 0
C18H3-01 0 0 0 0 0 0 0 0 0
C18H3-02 0 0.01 0 0 0 0 0 0 0
C18H3-03 0 0.03 0 0 0 0 0 0 0
C18H3-04 0 0.03 0 0 0 0 0 0 0
TGC14-01 0 0.09 0 0 0.01 0 0 0 0
TGC16-01 0 0.22 0 0 0.01 0 0 0 0
TGC16-02 0 0.02 0 0 0 0 0 0 0
TGC16-03 0 0.09 0 0 0.01 0 0 0 0
TGC16-04 0 0.08 0 0 0.01 0 0 0 0
TGC18-01 0 0.01 0 0 0 0 0 0 0
TGC18-02 0 0.04 0 0 0 0 0 0 0
TGC18-03 0 0.16 0 0 0.01 0 0 0 0
TGC18-04 0 0.15 0 0 0.01 0 0 0 0
H2O 0 0 0.01 0.01 0.14 0.01 0.43 0 0
CH4OH 0.01 0 0.65 0.65 0 0.64 0.37 0.36 0
CHCL3 0.98 0.01 0.34 0.34 0 0.33 0.2 0.19 0
234 Y. Peralta-Ruiz et al. / Applied Energy 101 (2013) 226236

Table 5
Specic chemical exergies of main components.

Component Specic chemical Component Specic chemical Component Specic chemical

exergy (kJ/kmol) exergy (kJ/kmol) exergy (kJ/kmol)
C14H2-01 8774870 TGC14-01 28019930
Cellulose 2834125 C16H3-01 10085570 TGC16-01 31948550
Lignin 5352170 C16H3-O2 9929620 TGC16-02 31480910
Hemicellulose 2313790 C16H3-03 9773740 TGC16-03 31013270
Aspartic 2079030 C16H3-04 9617860 TGC16-04 30545630
Glutamic 2475000 C18H3-01 11394270 TGC18-01 35877170
Glycine 1114980 C18H3-02 11174370 TGC18-02 52903360
Alanine 2000300 C18H3-03 11048870 TGC18-03 34941890
Valine 3307400 C18H3-04 10925044 TGC18-04 34474250
Leucine 3962170 C6H14-02 4114133.66 C2H6OH 1362935
Proline 3005530 H2O (liquid) 770 CHCL3 458386
Lysine 3900890 H2O (vapor) 9495 CH4OH 722115

it can be used for other applications such as bioethanol production

Table 6
Energy consumption of main equipment used in oil extraction routes evaluated.
Energy consumption (kW h)
Hydrocyclone 1 Hydrocyclone 2 Filter
HBE 74.25 0.5
EHE 14.3 6.3 0.5
SHE 53.4 0.5
ergy consumption corresponds to HBE route followed by SHE
route, As occurs in lab-scale, where lipid extraction efciency of
SHE route is higher than HBE, energy consumption can be de-
creased for HBE route since lower extraction efciencies implies
lower lipid ow to be pumped and separated from solvent, while
for SHE route, simulation shows a signicant energy consumption
which cannot be decreased if lab-scale extraction efciency is set
because of its capability for total lipid extraction and not for the
specic lipids needed for biodiesel production, for this reason
and from the energy consumption point of view, SHE method is
less convenient than other methods evaluated for a large-scale bio-
mass processing.
For all analyzed systems, the highest exergy inputs are repre-
sented by the microalgae biomass, solvents used and utilities;
among the greatest exergy outputs are the oil and residual bio-
mass. In this process, the residual biomass was considered as a
coproduct, due to its high content of carbohydrates and proteins
or as a dietary supplement; taking this into account, exergy losses
decreased substantially for waste streams. As shown in Fig. 5., the
highest exergy losses were occurred in the EHE route, specically
Pump in the oil extraction stage, being signicantly higher than HBE
21
and SHE, this difference can be explained by the amount of separa-
8.2 tion units required which increases exergy of utilities, heat and
13.1 work for the case of pumps increasing signicantly exergy inputs
of the route. The stage that shows more irreversibilities for all oil
extraction routes studied is the solids drying, with a total exergy
loss of 432,900 MJ for EHE; 321,041 MJ for SHE and 341,166 MJ
for HBE; also it is shown that biomass-solvent mixing stage pre-
sents the lowest exergy losses for all the three routes with values
of zero for EHE and HBE extraction routes.
EHE route presents the highest total exergy destruction of all
routes evaluated; this high exergy loss can be explained by the
additional equipment required to perform the route in a large scale
process in comparison to the equipment used in other routes eval-
uated in this work. Overall exergy efciency for each process was
also calculated, the total irreversibilities and the exergy of waste
for prot, these results are shown in Fig. 6. The hexane-based
extraction (HBE) shows the highest exergy efciency, lower total
irreversibilities, lower exergy losses for wastes, and lower utilities
required, while the EHE route has the highest exergies in each of
the categories quantied. Results show that for the three solvent-
based routes studied, the extraction with hexane HBE is the most

Fig. 5. Destroyed exergy by stage for microalgae oil extraction methods evaluated.
 Y. Peralta-Ruiz et al. / Applied Energy 101 (2013) 226236
Fig. 6. Exergy analysis results.
suitable for the extraction of oil from microalgae in a large scale
from the energy point of view, with a maximum exergetic
efciency of 51%, but they also demonstrate the need to reduce
waste and the amount of utilities in all three routes through meth-
odologies such as energy and process integration which could
diminish signicantly the overall irreversibilities of the processes.
Considerations made in this study related to oil extraction ef-
ciency does not have a signicant effect on exergy destruction and
process irreversibilities calculated for three microalgae oil extrac-
tion routes evaluated, since mass ow of solvents used, which rep-
resents a signicant exergy input, depends only of total biomass
processed, and does not depend on the amount of oil separated
from coproduct stream, likewise, exergy of wastes is not affected
by this consideration because streams of water after solvents
recovery for SHE and EHE routes remain constant. If extraction ef-
ciency decreases, solids stream will increase its exergy due to the
presence of oil not extracted, and exergy of oil stream will be low-
er, however overall exergy efciency of the process will not change
signicantly. The second assumption related to the presence of
homogeneous triglycerides in microalgae oil affects chemical exer-
gy of compounds and exergy of oil stream, issue which must be ta-
ken into account for transesterication process, but does not affect
in a great way exergy destruction during oil extraction. Also, exer-
gy of wastes is not affected by triglyceride prole because wasted
streams are free of these components. Exergy losses are affected by
hydrocyclons efciency assumed, because if this value decreases,
oil stream will need more equipment for product purication
increasing exergy destruction and utilities required, exergy of
wastes will be also affected by the presence of valuable biomass
components, however, for this reason, exergy efciency calculated
is taken as the maximum which can be reached by the systems
evaluated.
5. Conclusions
Application of exergy analysis for the evaluation of the use of
novel materials and routes for biomass processing for biofuels pro-
duction constitutes a useful tool for generating, screening and
designing alternatives towards sustainable development. Solvent
based routes for microalgae oil extraction were evaluated through
exergy analysis, showing that microalgae oil extraction with hex-
ane (HBE) is the most suitable of alternatives evaluated for an
oil-from-microalgae process on a large scale from the energy point
of view, obtaining by this route a maximum exergetic efciency of
51%. The highest exergy destruction for this route was found in sol-
ids drying stage, in addition, this route presents the lowest exergy
losses related to wastes, their utilities are less than other routes
235
studied and presents the lowest total irreversibilities
(981,978 MJ). Although this extraction route requires more elec-
tricity than other routes evaluated, this consumption is minimum
in comparison to other utilities as water and steam cooling. On the
other hand, ethanolhexane route (EHE) presented the lowest
exergy efciency (24%) of the routes evaluated, the highest exer-
getic losses of the extraction processes evaluated due to the neces-
sity of more mixing and extraction units than other methods,
increasing also energy losses related to heat transfer. Although
SHE route is commonly used in lab-scale for a rapid total lipid
determination on microalgae biomass, this route is not recom-
mended for a large scale process because presents high total irrev-
ersibilities, exergy of wastes and exergy of utilities, in addition,
SHE route also presents high potential environmental impacts
due to the use of chloroform and methanol.
Taking into account streams compositions, it is shown that
residual biomass after oil extraction must be used for downstream
processing because of its high exergy, even higher than oil exergy,
this biomass with high percentage of carbohydrates and proteins
can be used or cellulosic ethanol production or food and feed sup-
plements. It is recommendable for all routes evaluated to apply
optimization methodologies such as process integration, in order
to decrease utilities required for oil extraction processes and give
a positive use to waste and byproducts streams, studies related
to economics and environmental impacts and the development
of technical improvements for the stage of oil extraction in labora-
tory and pilot plant scale.
Acknowledgments
The authors thank the Ibero-American Program on Science and
Technology for Development (CYTED) project 306RTO279 New
technologies for biofuels production UNESCO codes 330303,
332205, 530603, 330999, the Colombian Administrative Depart-
ment of Science, Technology and Innovation COLCIENCIAS for sup-
porting this work through Francisco Jose de Caldas Scholarship
Programs, projects CT 475-2007, CT 272-2008, and creation and
strength of a knowledge and technology transfer network between
United States and Colombia for the development of biorenery
processes for obtaining biofuels and high value products from mic-
roalgae biomass.
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