Applied Energy 154 (2015) 815–828

Contents lists available at ScienceDirect

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

Process application of Subcritical Water Extraction (SWE) for algal

bio-products and biofuels production
Selvakumar Thiruvenkadam a, Shamsul Izhar a, Hiroyuki Yoshida a, Michael K. Danquah b, Razif Harun a,⇑
a
Department of Chemical and Environmental Engineering, Universiti Putra Malaysia, 43400 Serdang, Malaysia
b
Department of Chemical and Petroleum Engineering, Curtin University of Technology, 98009 Sarawak, Malaysia

h i g h l i g h t s

 We summarize the studies on subcritical water extraction of algae.

 Factors affecting biocrude yield, such as temperature and time, were reviewed.
 The produced biocrude evidence the future prospects of algal biofuels.
 Biocrude upgrading and scale-up strategies were too included in this paper.

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

Article history: Algal biomass is appreciated as an essential bioenergy feedstock owing to the rapid growth rate of algal
Received 20 November 2014 cells and the capacity to harbor substantial quantities of biochemicals via CO2 biosequestration for
Received in revised form 19 May 2015 biofuel production. Amongst the various thermochemical technologies for converting algal biomass to
Accepted 21 May 2015
biofuels, Subcritical Water Extraction (SWE) demonstrates significant capacity for generating liquid
transportation fuels from algae with minimal environmental impacts. The SWE process expends pressur-
ized water to produce biocrude or bio-oil as well as aqueous, solid, or gaseous by-products. However, the
Keywords:
existence of high levels of heteroatoms in biocrude hinders its application in internal combustion
Subcritical water extraction
Algae
engines, and this has triggered studies into parametric characterization of biocrude production from algal
Biocrude biomass. This article comprehensively reviews the process principles, optimal conditions, engineering
Bio-oil scale-up and products development to ascertain the viability of an industrial-scale SWE process for
Biofuels biofuel production from algae.
Thermochemical Ó 2015 Elsevier Ltd. All rights reserved.

Contents

1. Introduction . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 816
2. The theory of SWE . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 816
3. Biocrude . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 817
3.1. Factors affecting biocrude yield . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 817
3.1.1. Effect of temperature . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 817
3.1.2. Effect of residence time . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 819
3.1.3. Effect of water density and biomass loading . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 820
3.1.4. Effect of other solvent/co-solvents . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 820
3.1.5. Effect of catalyst . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 820
3.1.6. Effect of heating rate and stirring . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 821
3.1.7. Effect of algae strain. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 822
3.2. Energy recovery. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 822
3.3. Modeling and LCA analysis . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 824
3.4. Biocrude upgrading . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 824

⇑ Corresponding author. Tel.: +60 3 8946 6289; fax: +60 3 8656 7120.
E-mail address: mh_razif@upm.edu.my (R. Harun).

http://dx.doi.org/10.1016/j.apenergy.2015.05.076
0306-2619/Ó 2015 Elsevier Ltd. All rights reserved.
816 S. Thiruvenkadam et al. / Applied Energy 154 (2015) 815–828

3.5. Scale-up implications and recent developments . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 825

4. Other products . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 825
4.1. Aqueous product . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 825
4.2. Solid residue . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 826
4.3. Gas product . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 826
5. Conclusion . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 826
Acknowledgements . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 826
References . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 826

1. Introduction consumption [11]. Moreover, SWE process uses water which is a

cleaner solvent than chemical solvents, making it more favorable
Climate change, increasing energy consumption, growing in terms of environmental concerns and the lack of solvent recov-
human population and the development of new economies call ery operations [12]. Water plays a dual role as solvent and catalyst
for the creation of new and sustainable energy technologies such during SWE and after the reaction, water is recovered from the pro-
as biofuels [1]. The development of first and second generation bio- duct separator and recycled back into SWE process. A simple heat
fuels from proposed candidates, such as energy crops, lignocellu- integration system would economically help to scale-up this tech-
losic biomass, and agricultural wastes carry many demerits from nology by reducing energy penalty [13]. The main products of SWE,
a biodiversity and economic perspective [2]. In recent years, there biocrude or bio-oil, can be used as transportation fuel alone or
has been an increasing interest in algal biofuels, so-called third blended with petroleum diesel [14]. A body of work have been
generation biofuels. Algae are a unique biomass feedstock for sus- reported on the application of SWE for the extraction of essential
tainable production of biofuels. Algae, one of the fastest growing oils from coriander seeds [15], citrus fruit Yuzu [16], and herb zaa-
photosynthetic organisms on earth, have biomass productivity tar [17]; proteins and amino acids from deoiled rice bran [18];
rates higher than terrestrial plants [3]. They have several advan- antioxidant compounds from canola meal [19], and winery waste
tages including tolerance to extreme environmental conditions, [20]; phenolic compounds from bitter melon [21], and pomegra-
eco-friendly cultivation process, simple life cycle and resource nate [22]. The high moisture content of algal feedstock has made
availability for large-scale production [2–5]. Additional benefits SWE a promising technology to produce biocrude with minimal
of algae over food crops include fast growth rates, less water dewatering requirements. This article presents an overview of
intake, adaptation to various water sources (fresh, seawater, SWE process with bioprocess insights into the application of SWE
saline/brackish and wastewater), high photosynthetic efficiency, for the production of biofuels and bioproducts from algal biomass.
carbon dioxide (CO2) biosequestration, phytoremediation, inex-
pensive cultivation techniques using non-arable land and short
harvesting periods. Notwithstanding these benefits, algal biofuel 2. The theory of SWE
development faces a few drawbacks which include low biomass
densities and high operating costs for biomass generation and con- In SWE, water is pressurized to a temperature and pressure
version [6]. Although algal based biofuels generate approximately under its critical level conditions, described as the subcritical region
13% CO2 lower emissions from combustion relative to CO2 emis- according to Fig. 1. During SWE process, the feed slurry is processed
sions from petroleum diesel [7], in terms of absolute emission in a hot pressurized water system at a temperature between 100
levels, algal biofuels can be significantly high for full-scale applica- and 374 °C and a pressure of up to 22.1 MPa with or without the
tions. The development of biofuels from algal biomass has been presence of a reducing gas and/or catalyst [14,24]. The operating
significantly successful under lab-scale conditions. However, pressure is kept constant above the vapor pressure to hold the
opportunities for commercial-scale applications should focus on water in the liquid state at subcritical conditions. When operating
addressing related environmental, technological and economic below the vapor pressure, water boils to generate water vapor
drawbacks [2]. A wide variety of bioactive materials for pharma- and this vaporization process increases the pressure above the
ceutical, nutraceutical, and biomedical applications can be
extracted from algae. Apart from bio-oil, other products, such as
carbohydrates, polyunsaturated fatty acids (PUFAs), vitamins,
minerals, and dietary fibers, have been realized from algae.
Most existing technologies for production of algal biofuels pri-
marily aim on extracting lipids from algae and these technologies
involve downstream harvesting or dewatering processes such as,
flocculation and centrifugation [8]. However these processes are
expensive, energy intensive, unsustainable, involve lengthy
processing steps and result in lower product yields. Furthermore,
thermochemical conversion technologies, including gasification,
pyrolysis and Fischer–Tropsch process, require dry biomass and
operational temperatures higher than 600 °C [9]. Cost-effective
and energy-effective strategies play a key role in commercializa-
tion of algal biofuels. One of the newer technologies for generating
algal biofuels is Subcritical Water Extraction (SWE). The technique
involves liquefaction of high moisture content biomass containing
low solids (5–30%), with no requirement of energy-intensive cul-
ture dewatering and drying operations prior to extraction [10].
Unlike pyrolysis, SWE does not involve water volatilization, and
the technique is more preferable to pyrolysis in terms of energy Fig. 1. The phase diagram of water representing subcritical region [23].
 S. Thiruvenkadam et al. / Applied Energy 154 (2015) 815–828
vapor pressure level, resulting in the water being present in the
liquid state [25]. Besides the liquid state of water at subcritical
conditions, the increase in dielectric constant and the decrease in
density (1 g/cm3 at 25 °C to 0.75 g/cm3 at 300 °C) compared to
ambient conditions, result in hydrocarbons becoming more
water-soluble [26,27]. The decrease in density increases the dielec-
tric constant (relative permittivity; er), dissociation constant (Kw)
and diffusion, resulting from the breakdown of hydrogen-bonding
in the water molecule [27]. The polarity of water changes from
complete polarity to moderately non-polar in the subcritical
regions and this tends to increase the affinity of water toward
non-polar organic hydrocarbons [9]. Many acid- or base- catalyzed
reactions are accelerated at subcritical conditions due to high
concentrations of hydronium (H+) and hydroxide (OH ) ions,
derived from auto-ionization of water [12,28]. Close to critical
point, auto-ionization of water triples in order of magnitude
compared to ambient conditions; Kw of water increases from
10 14 at 25 °C to 10 11 at 250 °C and er of water decreases from
78.85 at 25 °C to 19.66 at 300 °C [9,27]. At these conditions, a
cascade of degradation and repolymerization reactions takes place
with the biomass, resulting in the establishment of a viscid liquid,
referred to as biocrude or bio-oil, which normally consists of
organic acids, various ketones and phenols. Other co-products from
SWE include aqueous products of dissolved organics, gas and solid
residue. Biocrude from SWE of algal biomass does not only contain
the lipid fraction, but also protein and carbohydrate fractions. The
degradation reactions transform the organic biomass into many
fragments which are converted to hydrocarbons by the addition
of hydronium ions to the existing open carbon bonds [9]. The
order of biocrude conversion efficiency during SWE process is:
lipids > protein > carbohydrates [29]. Biocrude, a precursor of
biodiesel, is the main product generally targeted from SWE of algal
biomass. After refining, the biocrude is used directly or
co-processed with petroleum diesel as a transportation fuel
[30,31]. Biocrude can also be used as the feedstock to produce other
bio-products such as resins and polyurethane foam materials [30].
After the SWE process, the products are cooled down, and this
restores water to its ambient ion concentrations, acting as a
self-neutralizing medium. This demonstrates the simplicity of
SWE process with the elimination of solvent recovery steps and
reducing waste production [27]. Recycling of aqueous products to
the algal cultivation system can be developed to provide a closed
loop bioprocess for the algal biorefinery paradigm. The proposed
scheme for the biorefinery model employing SWE process for
production of biofuel from algae is illustrated in Fig. 2 and reaction
mechanisms are also presented.
The schematic diagram of batch SWE process is shown in Fig. 3,
as depicted in Li et al. [14]. The setup consists of three main parts:
batch reactor with reactant(s) sampling and product(s) draining
ports, gas cylinder(s) and data recorder(s). The reactor is rinsed
with ethanol prior to the run. The feedstock(s) and extracting
solvent (water, ethanol or acetone) are loaded into the reactor
and closed tightly. The reactor headspace air is evacuated and
refilled with pure N2 [14] or He [5] gas for three cycles. The vessel
containing the reaction mixture is fitted with an electric heated
jacket for a defined residence time. The reactor is removed from
the bath and quenched with cold water [5]. Gaseous products can
be analyzed by connecting to a gas chromatographic unit before
depressurizing the system. The liquid product mixture is collected
from the reactor and subsequently cooled to yield three different
products: biocrude/bio-oil, aqueous product and solid residue.
3. Biocrude
Biocrude is an energy dense product derived from SWE of wet
biomass [32]. The algal biocrude has less dissolved water with
817
low density and provides a lower acid content (Total Acid
Number, TAN), in comparison to biocrude from liquefied lignocel-
lulosic biomass [33]. This makes algal biocrude advantageous for
biofuel development. However, algal biocrude is more viscous at
room temperature with high levels of nitrogen and sulfur. Bio-oil
from lignocellulosic biomasses can directly be used as heavy fuel
oil but the presence of high concentrations of oxygen and nitrogen
restricts its direct utilization as a transportation fuel. The conven-
tional petroleum hydroprocessing technologies can process algal
biocrude to hydrocarbon fuels similar to existing fossil petroleum
products [25]. The effects of physical and chemical parameters
on biocrude produced from SWE of algal biomass are discussed
in the following section.
3.1. Factors affecting biocrude yield
3.1.1. Effect of temperature
The most dominating operational parameter in SWE process is
temperature. High thermal energy released during elevated tem-
peratures increases the solvation power of the diluent or solvent
thereby overcoming cohesive and adhesive forces. High tempera-
tures contribute to decreasing water polarity [34]. This decrease
in polarity of water molecules at high temperatures favors
complete miscibility between lipids and water molecules, thus
increasing aqueous lipid extraction yield from algal biomass [35].
Close to the critical point (Tc = 374 °C and Pc = 22.1 MPa), the ionic
product of water increases, leading to hydrothermal breakage of
biomass into many fragments, favoring the increase in biocrude
yield with increasing temperature. However, with further temper-
ature increase, biocrude yield decreases as a result of the formation
of new compounds from degraded products. The formation of new
compounds is induced during condensation, polymerization and/or
cyclization reactions. Shuping et al. [24] observed the same results
when evaluating the effect of temperatures on biocrude yield of
Dunaliella tertiolecta. The optimum liquefaction temperature was
found to be 360 °C. Chen et al. [36] reported an increase in bio-
crude yield with increasing temperature up to 320 °C; with a fur-
ther increase in temperature resulting in the decomposition of
biocrude to gaseous products. During SWE of Chlorella pyrenoidosa
[37] and planktonic algae [38], oil yield notably increased with
increasing temperature from 260 °C to 280 °C, and a further
increase in temperature decreased the oil yield. Similar outcomes
were reported by Anastasakis and Ross [39], where biocrude pro-
duction increased with increasing temperature during SWE of
Laminaria saccharina. A threshold temperature of 340 °C was found
to maximize biocrude yield during hydrothermal co-liquefaction of
Spirulina platensis (microalgae) and Entermorpha prolifera (macroal-
gae) [40]. It was understood that the synergistic effect on biocrude
productivity during liquefaction of both algal strains is influenced
by temperature.
Plaza et al. [41] reported the influence of temperature on
extraction yield while characterizing bioactive compounds from
the green alga Chlorella vulgaris by SWE and Ultrasound-Assisted
Extraction (UAE) techniques. It was shown that the extraction
yields were higher in SWE than UAE and this was attributed to
the increased mass transfer in SWE. Moreover, the highest yield
and the maximum antioxidant activity were recorded at the high-
est temperature examined (200 °C). SWE with different solvents
showed that extraction with water resulted in high yields of
antioxidant compounds compared to ethanol and acetone. The
antioxidant activity of the water extracts increased with increasing
temperature, but this trend was not observed with the acetone and
ethanol extracts. However, generally, the diffusion coefficients of
the compounds increase with increasing extraction temperature
and this favors desorption kinetics from the cellular matrix [42].
818 S. Thiruvenkadam et al. / Applied Energy 154 (2015) 815–828

Fig. 2. Algae biorefinery model featuring SWE.

High aqueous phase and solid residue yields accompanying low phase and solid residue yields [44]. Eboibi et al. [45] examined
yields of biocrude and gas are usually noted at low temperatures the effect of temperature on SWE of Tetraselmis species.
due to hydrolysis reactions [43]. However, increasing temperature Increasing the reaction temperature from 330 °C to 350 °C for
shows increasing biocrude and gas yield with decreasing organic 5 min increased the biocrude yield. However, increasing the
 S. Thiruvenkadam et al. / Applied Energy 154 (2015) 815–828
Fig. 3. A schematic drawing of a typical batch scale SWE process. Source: Li et al. [14]; reprinted with permission.
temperature further favored gasification reactions to increase gas
yield. High temperatures (330–340 °C) were found to be optimal
for rapid degradation of proteins and carbohydrates, and biocrude
formation at these conditions are favored with rapid heating and
cooling rates [46]. It has also been demonstrated that different
operating conditions can promote the conversion of individual bio-
chemical components. On comparing SWE of freshwater
Oedogonium sp. and marine Derbesia tenuissima, Neveux et al.
[46] concluded that the biocrude production is dependent on the
organic fraction of the algae regardless of its origin, freshwater or
marine environment. The extent of depolymerization, cracking
and repolymerization during SWE is influenced by the reaction
conditions [43]. It is unclear if the three main reactions (hydrolysis,
cracking and polymerization) happen sequentially or simultane-
ously to produce biocrude or bio-oil. To understand the cell break-
age point during SWE, Garcia-Alba et al. [44] visually monitored
Desmodesmus sp. cells after SWE using scanning electron micro-
scopy (SEM). The changes in algal cell morphology were correlated
with the differences in biocrude yield. At 225 °C, the cells were
found to be distorted and closely filled with some solid molecules,
which are probably from adhesions of intracellular denatured pro-
teins and/or maillard reactions producing melanoidins. The pres-
ence of algaenan in green algae such as Desmodesmus sp.
provides thermal resistance to the cell wall at higher temperatures,
thus denaturation of intracellular components can occur without
cell wall breakage. After increasing the temperature to 250 °C,
the visually compact cells at 225 °C ruptured to release intracellu-
lar components.
Valdez et al. [47] investigated the effects of temperature, reac-
tion time, water densities, and biomass loadings on the yields
and elemental analyses of the product fractions from SWE of
Nannochloropsis sp. in mini-batch reactors under sub- and
super-critical conditions. The biocrude yields at subcritical temper-
atures (300 °C and 350 °C) were higher compared to the yields at
250 °C and 400 °C. A steady increase in the yield of light biocrude
was observed with increasing temperature above 300 °C. In con-
trast, the yield of heavy biocrude decreased above 300 °C, resulting
from the polymerization reactions and/or the conversion of heavy
biocrude to light biocrude. Extract viscosity is used to distinguish
between heavy and light biocrude. The formation of water soluble
products decreased with increasing process time at 300 °C and
350 °C, and this decrease was validated by the increase of volatile
compounds, indicating the decomposition of aqueous phase com-
pounds to volatile compounds. Increasing yields of gases (H2, CO,
819
CO2, CH4, C2H4 and C2H6) were observed with increasing process
time and temperature. Jin et al. [48] studied the SWE behavior of
C. pyrenoidosa in an acetone medium under sub- and
super-critical conditions (Tc = 235 °C and Pc = 4.8 MPa). A decreas-
ing trend in biocrude yield was observed with increasing temper-
ature. The decrease in biocrude yield was accompanied by a
increase in solid yield. Compared to water, liquefaction of algae
in acetone occurs at milder conditions with a trade-off in biocrude
quality including high viscosity and high nitrogen content.
3.1.2. Effect of residence time
In a study to investigate the effect of residence time on SWE of
L. saccharina, 15 min was found to be the optimum holding time at
350 °C and further increase in residence time decreased biocrude
yield due to subsequent condensation and/or polymerization of
biocrude intermediates to form new high molecular weight prod-
ucts [39]. This was supported by Xu et al. [38], Jin et al. [40] and
Shuping et al. [24], who observed decreasing in biocrude yield
beyond the threshold points 30 min, 40 min and 50 min respec-
tively. Also, a short residence time during SWE increases biocrude
yield due to the rapid release of the intracellular components of the
biomass [45]. A short residence time is beneficial to reduce the
costs for commercial scale applications involving small reactors.
However, Eboibi et al. [45] and Jazrawi et al. [26] reported that
shorter residence times, though produce high biocrude yield, gen-
erates low quality biocrude due to high oxygen content.
Notwithstanding, Shuping et al. [24] discovered a consistent
increase in oil yield up to 60 min residence time during SWE of
D. tertiolecta. With increasing residence time, the aqueous phase
and solid residue showed a gradual decrease while the gaseous
yield gradually increased. Tsigie et al. [31] showed that the fatty
acid methyl ester (FAME) yield increased with increasing reaction
time during SWE for biodiesel production from C. vulgaris. It has
also been suggested that a longer residence time is essential to
increase FAME yield, and the series of process steps takes place
in the order: cell wall breakage, release of lipids out of the cell,
and reaction of lipids with methanol [31]. Longer retention times
are recommended for repolymerization of small organic materials
formed from protein hydrolysis [49]. On the contrary, longer reten-
tion times do not affect the lipid extraction recovery from algal bio-
mass [50]. Garcia-Alba et al. [44] demonstrated that at a
moderately low temperature (200 °C), a longer residence time
causes thermal degradation of intracellular constituents without
rupturing the cell wall, resulting in oil yield increase as well as
820 S. Thiruvenkadam et al. / Applied Energy 154 (2015) 815–828
the composition of N and C elements. It was also found that shorter
residence times increase biocrude yield at temperatures above
300 °C. In another set of experiments carried out at higher heating
rates 585 °C/min [10], the residence time was varied within the
range 5–20 min to find the optimum retention time. It was noted
that neither a shorter nor longer residence time outside the range
investigated increased the biocrude yield. The maximum biocrude
yield (79%) was obtained at 15 min residence time. While studying
the bio-oil distribution after SWE of Desmodesmus sp. [44], the
bio-oil yield doubled with increasing reaction time from 5 to
60 min at a low temperature (200 °C). However, a slight increase
in bio-oil yield was observed for the same variation in reaction
time at a higher temperature (300 °C).
3.1.3. Effect of water density and biomass loading
The quantity of water in the extraction system is another crucial
parameter that influences biocrude yield. The presence of water
could act as a green solvent, hydrolyzing agent, catalyst, and
hydrogen donor [39,40]. Maximum biocrude yield was achieved
at an optimum reactor loading of 1:10 ratio (biomass: water,
g/mL) from SWE of the brown alga L. saccharina [39], and further
increase in water ratio did not affect the biocrude yield. This find-
ing has been supported by Jin et al. [40] after studying the influ-
ence of algal biomass/water ratio on co-liquefaction of S.
platensis/E. prolifera. The maximum biocrude yield was obtained
at 1:5.8 ratio (biomass:water, g/g), and a further increase in this
ratio decreased biocrude yield. The dilution of biocrude precursors
at higher water loadings does not support further polymerization
reactions. According to the experimental results from SWE of C.
pyrenoidosa [37], the yield of bio-oil decreased with increasing
total solid ratio from 15% to 25%. However, the contrary was
observed with further increase in total solids from 25% to 35%. It
was established that total solid ratio had no effect on the higher
heating value (HHV) of the biocrude or bio-oil produced.
However, it had a positive effect on carbon and nitrogen contents
of the biocrude. Co-liquefaction of microalgae/cyanobacteria and
macroalgae was demonstrated in a 20 mL stainless steel reactor
by Jin et al. [40]. The effect of both algae mass ratios on biocrude
yield was monitored by varying the mass ratio (S. platensis and E.
prolifera) from 0% to 100%. The highest biocrude yield was achieved
at a mass ratio of 50%, and any further increase in the mass ratio
reduced the synergetic effect. The authors also reported that fatty
acids produced from S. platensis promoted the hydrolysis of pro-
teins and carbohydrates in E. prolifera. Garcia-Alba et al. [44] inves-
tigated the effect of algal concentration on biocrude yield and the
result showed that the increase in algae loading rate did not have
a significant effect on biocrude yield. Pham et al. [51] presented the
liquefaction behavior of Spirulina on the removal of bioactive com-
pounds. The results indicated that the removal of bioactive com-
pounds (ceftiofur and florfenicol) decreased with increasing solid
concentration of Spirulina.
3.1.4. Effect of other solvent/co-solvents
The introduction of ethanol as the extracting solvent instead of
subcritical water in SWE resulted in a slight increase in biocrude
yield and quality under H2 as the processing gas [52]. Chen et al.
[50] attempted subcritical co-solvents extraction (SCE) of
Nannochloropsis sp. at 90 °C, 1.4 MPa and 50 min with a mixture
of hexane and ethanol. They also optimized the extraction condi-
tions such as the hexane to ethanol (3:1) ratio and the
co-solvents to microalgae (10:1) ratio. Hexane enhanced the
extraction efficiency by displacing of the largely non-polar lipids
into the hexane phase from the lipid carrier, ethanol. In the pres-
ence of organic solvents, the extraction efficiency increases with
increasing temperature and pressure, and this is due to decreasing
viscosity of the solvent, increasing lipid solubility and decreasing
ethanol polarity. Alcohol is a reactant for in situ transesterification
process to produce biodiesel [31]. It is used to convert lipids to
fatty acid alkyl esters, and also considered as an extracting solvent
for lipids extraction from biomass. The effect of methanol concen-
tration on extraction efficiency has been reported by Tsigie et al.
[31]. Increasing methanol to algal biomass ratio increased the con-
version rate of biocrude lipids to biodiesel until a maximum yield
is achieved, and a further increase in the ratio decreased FAME
yield.
3.1.5. Effect of catalyst
Catalyst addition during SWE has generated a steady interest
since they are expected to enhance biocrude yields. Comparative
studies on the effect of organic acid (CH3COOH and HCOOH) and
alkali (KOH and Na2CO3) catalysts on SWE of C. vulgaris and
Spirulina displayed higher yields of bio-oil at higher temperatures,
and the yield was higher for lipid-rich C. vulgaris compared to
Spirulina [53]. It is generally assumed that lipid-rich algae produce
more biocrude, and this was verified by Toor et al. [54] during SWE
of Nannochloropsis salina, producing the highest biocrude yield of
46% at 350 °C. In their study, Shuping et al. [24] evaluated the
effect of Na2CO3 catalyst on the liquefaction of D. tertiolecta and
obtained the optimum biocrude yield in the presence of 5%
Na2CO3. High-carbohydrate algae are probably the most efficiently
liquefied with Na2CO3 catalyst. These carbohydrates break down
precursors for biocrude formation. However, in the case of
high-lipid algal species, Na2CO3 has a negative effect on oil yield
due to the formation of soap between algal lipids and alkaline,
causing serious biochemical and process challenges to biodiesel
production [31,49]. Zeolite catalyst types, raney-Ni and HZSM-5,
produced no significant results during SWE of C. pyrenoidosa with
ethanol as the solvent [52]. The inexpensive catalyst zeolite
HZSM-5 was tested for treating crude bio-oil from SWE of
Nannochloropsis sp. [55]. Three parameters namely reaction tem-
perature, reaction time and catalyst loading were examined and
it was found that the reaction temperature had a significant effect
in the treated bio-oil composition compared to the other
parameters.
Biller et al. [56] studied the effect of three catalysts (Pt/Al2O3,
Ni/Al2O3 and Co/Mo/Al2O3) during SWE of C. vulgaris and
Nannochloropsis occulta. Among the catalysts tested, Co/Mo/Al2O3
increased biocrude yield from C. vulgaris by 3 wt.% while the bio-
crude yield from N. occulta decreased by 10 wt.%. A similar trend
was obtained for the Pt/Al2O3 catalyst. Ni/Al2O3 catalyst decreased
biocrude yield from both algal species due to hydrogen formation
promoted by increased decarboxylation and gasification reactions.
Algal biocrudes derived from these heterogeneous catalysts con-
tain no alkanes, indicating the deoxygenation of protein and carbo-
hydrate fractions of the algal species. Anastasakis and Ross [39]
tested KOH catalyst and found that the biocrude yield decreased,
with a significant increase in the solubility of organic compounds
in the aqueous phase. The addition of organic acid and alkaline cat-
alysts to SWE of C. vulgaris and Spirulina was shown to improve the
heat content of bio-oils [53]. The alkaline catalyst increased the
heat content slightly higher than the organic acid. Furthermore,
it was found that the organic acid catalyst reduced the boiling
point and increased the flow properties of the bio-oil.
Yu et al. [57] evaluated the effect of five heterogeneous (Pd/C,
Pd/Al2O3, Pt/C, Pt/Al2O3 and Raney Nickel) and two alkaline
(NaOH and Na2CO3) catalysts on SWE of C. pyrenoidosa. The cat-
alyzed SWE analyses at 240 °C produced no significant increase
in biocrude yield except NaOH. However, all the catalysts produced
more significant results at 280 °C. The overall effect of catalyst
presence on biocrude yield was not overwhelmingly high, and this
likely due to instability of the catalysts under SWE operating con-
ditions. To study the effect of catalyst dosage, the authors utilized
 S. Thiruvenkadam et al. / Applied Energy 154 (2015) 815–828 821

5% and 30% Pt/Al2O3 at the same SWE conditions. They observed
that the catalyst dosage did not affect the biocrude yield. The study
also established that pre-reduction of metal catalysts is unneces-
sary as oxygen is removed from fatty acids by decarboxylation.
The catalysts were found to be less effective on the boiling point
distribution of biocrude. Also, the elemental composition of bio-
crude did not considerably change after catalyst application. The
heterogeneous catalysts increased the hydrocarbon fractions in
biocrude (except for Pd/Al2O3) and decreased the organic acids
fraction. The compositions of amides, nitrogen and oxygen hetero-
cyclic compounds were not affected by the heterogeneous cata-
lysts. The alkaline catalysts increased the N and O heterocyclic
compounds, probably due to polymerization of oil intermediates
promoted by hydrogen ions which are dissociated from fatty acids.
The effect of various catalysts on biocrude yield is presented in
Table 1. The possibility of carbon deposition on the surface of the
catalysts were investigated using environmental scanning electron
microscopy (ESEM) [57]. This is essential for repeated use of the
catalysts. To minimize catalytic poisoning by algal feedstock,
Yang et al. [5] proposed a two-chamber reactor, where the algal
feedstock and the catalyst (Pt/C) are loaded into each chamber.
The chambers were separated by a porous metal frit to allow free
flow of molecules between the chambers. This arrangement was
compared with the conventional method of loading algal feedstock
with catalyst presence in a single-chamber reactor. SWE of
Nannochloropsis sp. from the two-chamber reactor produced a
slightly better biocrude yield than the conventional
single-chamber reactor setup. This slight increase in biocrude yield
is due to the reduction of catalyst deactivation from algal biochem-
icals. SWE of Nannochloropsis sp. at 350 °C for 60 min under H2
(30 bar) atmosphere produced 80% of light biocrude resulting from
hydrogen-promoted catalytic reactions such as hydrogenation and
hydrodeoxygenation. Li et al. [14] studied the effect of hydrogena-
tion on SWE of N. salina. For hydrogenated SWE under Ni–
Mo/Al2O3 catalyst, a biocrude yield of 78.5% was reported, and this
was higher than those reported for non-hydrogenated SWE
(55.6%). In addition, the hydrogenation process produced less gas-
eous products. Bach et al. [10] reported a different effect of catalyst
(KOH) addition on biocrude yield of seaweed L. saccharina. They
obtained a slight increase in biocrude yield 2%. However, this
study was carried out at higher heating rates (585 °C/min) using
reactors with relatively small volumes.
3.1.6. Effect of heating rate and stirring
Bach et al. [10] carried out the optimization of SWE of L. saccha-
rina by using small quartz capillary reactors at different heating

Table 1
Summary of elemental compositions and calorific values of fresh algae and biocrudes produced from catalyzed SWE processes.

Algae Feedstock Biocrude SWE Reference

conditions
Elemental Compositiona HHVb Elemental Compositiona HHVb Yieldc Tempd Timee
C H N O S C H N O S
Catalyst: Na2CO3
Chlorella vulgaris 52.6 7.1 8.2 32.2g 0.5 23.2 73.6 10.7 4.9 10.7g 0 37.1 30 350 60 [49]
Dunaliella tertiolecta 39f 5.37f 1.99f 53.02f,g ND 20.08 63.55f 7.66f 3.71f 25.08f,g ND 30.74 25.8 360 5 [24]
Nannochloropsis oculata 57.8 8 8.6 25.7g NA 17.9 69.6 9.2 3.8 17.3g 0 35.5 28 350 60 [49]
Porphyridium cruentum 51.3 7.6 8 33.1g NA 14.7 46.1 5.6 3.2 13.3g 0.2 22.8 30 350 60 [49]
Spirulina sp. 55.7 6.8 11.2 26.4g 0.8 21.2 75.4 10.8 4.6 8.7 0.5 34.8 18 350 60 [49]
Catalyst: HCOOH
Chlorella vulgaris 53.6 7.3 9.2 29.4g 0.5 23.2 72.1 9.5 6.4 11.5g 0.5 35 22h 300 60 [53]
Chlorella vulgaris 52.6 7.1 8.2 32.2g 0.5 23.2 70.8 9.4 5.3 13.9g 0.6 33.2 30 350 60 [49]
Nannochloropsis oculata 57.8 8 8.6 25.7g NA 17.9 74.7 10.6 4.3 10.4g 0 39 28 350 60 [49]
Porphyridium cruentum 51.3 7.6 8 33.1g NA 14.7 72.5 9.1 5.7 13.3g 0.4 36.3 20 350 60 [49]
Spirulina sp. 55.7 6.8 11.2 26.4g 0.8 21.2 72.7 9.8 5.7 10.9g 1 35.1 22 350 60 [49]
Spirulina sp. 54.4 7.6 10.9 26.3g 0.83 21.2 72.7 9.8 5.7 10.9g 1 35.6 14.2h 350 60 [53]
Catalyst: CH3COOH
Chlorella vulgaris 53.6 7.3 9.2 29.4g 0.5 23.2 70.8 9.4 5.3 14.1g 0.4 34.2 23h 300 60 [53]
Spirulina sp. 54.4 7.6 10.9 26.3g 0.83 21.2 71.7 9.7 6.1 11.6g 0.9 35.1 16.6h 350 60 [53]
Catalyst: KOH
Chlorella vulgaris 53.6 7.3 9.2 29.4g 0.5 23.2 74 12.9 4.3 8.9g 0.2 39.9 22.4h 350 60 [53]
Spirulina sp. 54.4 7.6 10.9 26.3g 0.83 21.2 74.6 11.4 5.1 8.5g 0.5 33.4 15.2h 350 60 [53]
Catalyst: Pt/Al2O3
Chlorella vulgaris 52.6 7.1 8.2 32.3g 0.5 23.3 74.8 9.7 5.6 9.3g 0.6 37.9 38.9h 350 60 [49]
Nannochloropsis occulta 57.8 8 8.6 25.7g ND 17.9 74 10.2 3.6 12g 0.1 38.2 30.2h 350 60 [49]
Catalyst: Ni/Al2O3
Chlorella vulgaris 52.6 7.1 8.2 32.3g 0.5 23.3 75.4 6.7 5.4 12.6g 0 34.5 30.0h 350 60 [49]
Nannochloropsis occulta 57.8 8 8.6 25.7g ND 17.9 76.8 9.4 3.6 10.2g 0 38.2 18.1h 350 60 [49]
Catalyst: Co/Al2O3
Chlorella vulgaris 52.6 7.1 8.2 32.3g 0.5 23.3 75.2 8.3 5.7 10.7g 0 36.2 38.7h 350 60 [49]
Nannochloropsis occulta 57.8 8 8.6 25.7g ND 17.9 77 8.9 4.6 9.4g 0 37.6 25.5h 350 60 [49]
Catalyst: Ni–Mo/Al2O3
Nannochloropsis salina 56.52 8.28 8.51 26.69g 24.17 73.46 10.31 4.88 11.35g 37.53 78.5h 340 30 [14]
a
wt.%, ash-free dry weight.
b
Higher heating value, MJ/Kg.
c
wt.%, dry weight.
d
temperature, °C.
e
time, min.
f
wt.%, dry weight.
g
Calculated by difference.
h
wt.%, ash-free dry weight.
822 S. Thiruvenkadam et al. / Applied Energy 154 (2015) 815–828

rates (146 °C/min, 321 °C/min and 585 °C/min). The study was
aimed to minimize the heat and mass transfer limitations. At the
highest heating rate of 585 °C/min, the maximum biocrude yield
of 79% was achieved while the biocrude yield of 53% and 65% were
obtained at heating rates of 146 °C/min and 321 °C/min respec-
tively. They also concluded that higher heating rates are more
favorable in enhancing biocrude yield than the utilization of cata-
lysts. The beneficial effects of rapid heating [10] are: (i) accelerat-
ing degradation reactions, (ii) limiting unwanted reactions, (iii)
facilitating cell disruption, and (iv) preventing biochar formation.
In the case of lignocellulosic compounds, heating and cooling rate
are characterized as crucial parameters during liquefaction [58].
The effect of stirring has been demonstrated to have a negligible
effect on biocrude yield [31]. Stirring is mostly considered during
SWE to avoid clustering of biomass, and also to make biomass
accessible to methanol during in situ transesterification [31]. The
authors also confirmed that biomass stirring at lower temperatures
provided better results with simultaneous extraction and transes-
terification of wet microalgal biomass.
3.1.7. Effect of algae strain
The production of biofuels from algal biomass is influenced by
both biological (e.g. algal cell morphology, growth conditions such
as, temperature, nutrients and photo period) and technological
(cultivation, harvesting, extraction and/or conversion) factors
[59]. As presented in Fig. 4, biochemical composition varies
between algae species. Neveux et al. [46] reported a low biocrude
yield from the marine alga Chaetomorpha linum and this is partly
due to its high inorganic content (36.6 wt.% ash and 5.1 wt.% mois-
ture). Algae species with high inorganic content are recognized as
undesirable for SWE as they result in low biocrude yields. Ash con-
tent in algal biomass could be reduced by either selected culture or
post-harvest processing [46]. Chen et al. [64] proposed a two-step
pretreatment method, centrifugation followed by ultrasonication,
to reduce ash content and increase biocrude yield for a
mixed-culture wastewater algae (WA). Centrifugation segregates
the volatile matter from ash while the ultrasonication process
breaks down volatile mater into individual components by
cavitation.
The biochemical composition and the structural characteristics
of the cell wall affect the SWE process and the corresponding bio-
crude yield. Algal strains with no or reduced cell wall (e.g.
Phaeodactylum tricornutum and D. tertiolecta) produce more bio-
crude yield at mild SWE conditions compared to species with
strong cell walls (e.g. Scenedesmus obliquus) [65]. Under harsh
and severe SWE conditions, strain-specific parameters are less
influential on biocrude yield. Reddy et al. [35] carried out SWE of
two algal species, Chlorella sorokiniana and D. tertiolecta, cultivated
in tap water and geothermal water media. They studied SWE of
biocrude oil by comparing biocrude oil yield and lipid content.
The alga D. tertiolecta cultivated in tap water produced the maxi-
mum biocrude oil of 30%. Comparison between biocrude oil yield
and lipid content showed that the biocrude oil yield was higher,
probably due to protein hydrolysis. The highest heating value
(38 ± 1.8 MJ/kg) of biocrude oil was obtained from D. tertiolecta
cultivated in geothermal water. The elemental analyses and HHV
of some selected algae and their biocrude compositions are tabu-
lated in Table 2. Zhu et al. [67] reported a high efficiency of SWE
in converting lipid-extracted algae (LEA) to biofuels using a bench
scale continuous SWE reactor, and the resulting bio-oil was
upgraded by hydrocracking and hydrotreating. Li et al. [66] carried
out SWE on two algal strains, Nannochloropsis sp. and Chlorella sp.,
with varying lipid/protein compositions. They investigated the
influence of temperature, extraction time and total solid content
of the feedstock. Algal feedstock compositions greatly influenced
the SWE performance. The results also imply that the hydrother-
mal conversion process is not only affected by lipid content. They
also concluded that algal biomacromolecules greatly influence
bio-oil yield and quality.
3.2. Energy recovery
The energy recoveries reported for the biocrudes of Oedogonium
sp., U. ohnoi, D. tenuissima, Cladophora vagabunda, C. coelothrix and

lipid protein carbohydrate

Chaetomorpha linum
Chlorella sorokiniana
Chlorella vulgaris
Chlorogloeopsis fritschii
Cladophora coelothrix
Cladophora vagabunda
Derbesia tenuissima
Dunaliella terolecta
Enteromorpha prolifera
Gelidium amansii
Nannochloropsis oceania
Nannochloropsis salina
Nnannochloropsis occulta
Oedogonium sp.
Porphyridium cruentum
Scenedesmus dimorphous
Spirulina sp.
Spirulina platensis
Tetraselmis sp.
Ulva fasciata
Ulva ohnoi

0 20 40 60 80 100 120

Biochemical composion (%)

Fig. 4. Biochemical composition (%) of different species of algae [35,40,45,46,49,54,56,60–63].

 S. Thiruvenkadam et al. / Applied Energy 154 (2015) 815–828 823

Table 2
Ultimate analysis and higher heating values of different algae strains and their corresponding biocrudes.

Algae Feedstock Biocrude SWE Reference

conditions
Elemental Compositiona HHVb Elemental Compositiona HHVb Yieldc Tempd Timee
C H N O S C H N O S
Chaetomorpha linum 26.5 4.1 3.4 31 2.1 10.3 70.9 7.7 6.8 11.4 0.1 32.5 9.7 330 5 [46]
Chlorella sp. 53.5f 7.4f 11f 27.6f,g 0.5f 24.3 70.7f 8.8f 7.7f 12.0f,g 0.8f 33.8 41.7 350 3 [26]
Chlorella sp. 60.5 9.1 1.9 21.8 32.3 75.6 12 0.3 11.5 34.2 82.9 220 90 [66]
Chlorella vulgaris 42.3 5.1 6.2 0.4 70.6 9.2 5.5 12.3 0.4 34.4 33 250 5 [65]
Chlorella vulgaris 52.6f 7.1f 8.2f 32.2f,g 0.5f 23.2 70.7f 8.6f 5.9f 14.8f,g 0 35.1 40 350 60 [49]
Chlorella vulgaris 52.6f 7.1f 8.2f 32.3f,g 0.5f 23.2 70.7f 8.6f 5.9f 14.8f,g 0 35.1 35.8h 350 60 [56]
Cladophora coelothrix 30.9 5 5.2 34.9 2.3 12.7 71.6 8 7.1 10.6 0.9 33.3 13.5 330 5 [46]
Cladophora vagabunda 37.5 5.9 6.5 32.9 1.8 16.4 71.1 8.3 6.8 10.6 1.3 33.5 19.7 330 5 [46]
Derbesia tenuissima 29.2 4.8 4.5 27.4 2.8 12.4 73 7.5 6.5 10.6 0.7 33.2 19.7 330 5 [46]
Desmodesmus sp. 51.96f 7.31f 6.86f 33.87f,g 23.44 75.8f 9.1f 6f 9.1f 36.6 46.5 350 60 [44]
Dunaliella tertiolecta 51.9 7.5 8.6 0.5 71.3 9.1 5.3 12.2 0.4 34.6 44.8 250 5 [65]
Gelidium amansii 28.04 4.85 2.62 64.48g 9.8 78.46 10.24 4 7.3g 40 11.98 350 20 [61]
Laminaria saccharina 39.44f 5.14f 2.99f 52.03f 0.6f 14.46 75.54f 9.16f 3.65f 11.66f 0.62f 35.97 79h 350 15 [10]
Laminaria saccharina 31.3 3.7 2.4 26.3 0.7 12 82 7.1 4.9 5.4g 36.5 19.3 350 15 [39]
Mixed culture algae 27.9 3.01 3.9 65.2g 0.4 12.9 59.4 7.79 2.50 30.3 g 25.8 300 60 [32]
Nannochloropsis gaditana 51 6.6 6.9 0.4 71.5 9.7 3.7 11.5 0.2 35.4 34.4 250 5 [65]
Nannochloropsis occulta 57.8f 8f 8.6f 25.7f,g ND 17.9 68.1f 8.8f 4.1f 19f,g 0 34.5 34.3h 350 60 [56]
Nannochloropsis oceanica 50.06 7.46 7.54 34.47g 0.47 21.46 72.58 9.75 5.09 12.06g 0.52 36.35 40.08 300 30 [60]
Nannochloropsis oculata 57.8f 8f 8.6f 25.7f,g NA 17.9 68.1f 8.8f 4.1f 18.9f,g 0 34.5 38 350 60 [49]
Nannochloropsis salina 55.16 6.87 2.73 33.97g 1.27 25.4 77.2 9.01 2.75 8.71 1 38.1 350 30 [54]
Nannochloropsis salina 56.52 8.28 8.51 26.69g 24.17 72.59 9.79 5.2 12.42g 36.3 55.6 340 30 [14]
Nannochloropsis sp. 43.7 7.7 7.5 29.1 22.4 74 10.2 5.4 9.5 31.5 55.0 260 60 [66]
Oedogonium sp. 36.6 5.7 4.8 30.9 0.4 15.8 72.1 8.1 6.3 10.4 0.8 33.7 26.2 330 5 [46]
Phaeodactylum tricornutum 38 4.8 5.2 0.7 62.9 8 4.7 12 0.3 30.3 40.8 250 5 [65]
Porphyridium cruentum 51.3f 7.6f 8f 33.1f,g NA 14.7 72.8f 8.5f 5.4f 13.3f,g 0.4f 35.7 22 350 60 [49]
Porphyridium purpureum 45.6 6.1 6 1.1 69.1 8.4 5 15.2 0.5 32.7 24.7 250 5 [65]
Scenedesmus almeriensis 50.6 6.4 6.8 0.4 72.6 9.4 4.1 12.5 0.3 35.3 35.7 250 5 [65]
Scenedesmus obliquus 44.4 5.4 5.8 0.3 69.3 9.1 5.1 12.9 0.2 33.8 17.6 250 5 [65]
Spirulina sp. 53.7f 7.7f 12.1f 25.9f,g 0.6 24.9 68.3f 8.3f 6.9f 15.4f,g 1.1f 32 300 5 [26]
Spirulina sp. 55.7f 6.8f 11.2f 26.4f,g 0.8 21.2 73.3f 9.2f 7f 10.4f,g 1f 36.8 34 350 60 [49]
Spirulina platensis 42.26 5.86 3.47 47.26g 1.15 20.4 70.69 8.05 7.22 10.06 0.77 34.3 350 30 [54]
Tetraselmis sp. 42 6.8 8 40.2g 3 19.2 71 9.5 5 14g 0.6 35 65 350 5 [45]
Tetraselmis suecica 45 5.9 6.3 1.1 62.6 7.4 4.8 14 0.4 29.3 29.4 250 5 [65]
Ulva ohnoi 27.7 5.5 3.5 41.4 5 11.7 72.6 8.2 5.8 11 0.4 33.8 18.7 330 5 [46]
a
wt.%, dry weight.
b
Higher Heating value, MJ/Kg.
c
wt.%, dry weight.
d
Temperature, °C.
e
Time, min.
f
wt.%, ash-free dry weight.
g
Calculated by difference.
h
wt.%, ash-free dry weight.

C. linum were 55.7%, 54%, 52.5%, 40.1%, 35.3% and 30.6% respec-
tively [46]. Energy recoveries of 38–87% and 52.5% were obtained
from biocrudes of Tetraselmis sp. [45] and mixed-culture algal bio-
mass [36] respectively. Another similar study on a mixed-culture
algal biomass and swine manure mixture produced an energy
recovery of 49.9% and also promoted net energy gain [32]. The bio-
crude from S. platensis co-liquefied with E. prolifera contained
higher nitrogen and lower oxygen contents [40]. Moreover, this
co-liquefaction enhanced the conversion of proteins in the algal
biomass.
Eboibi et al. [45] obtained up to 63–88% and 24–53% for carbon
and nitrogen recovery respectively in the biocrude from SWE of
Tetraselmis species. Low nitrogen recovery (8.41–16.8%) was
obtained from the biocrude of mixed-culture algal biomass, and
this is probably due to the presence of calcium carbonate in the
feedstock [36]. While comparing the effect of various heteroge-
neous and alkaline catalysts on recovery, Yu et al. [57] reported
the highest carbon recovery from the biocrude of C. pyrenoidosa
in the presence of alkaline catalyst NaOH at 240 °C. However, the
carbon content in biocrude from NaOH-catalyzed SWE (68.3%)
was lower than that obtained from non-catalyzed SWE (75.7%) at
240 °C. At 280 °C, the carbon recovery of biocrude from catalyzed
SWE was higher than that obtained from non-catalyzed SWE.
They also noted that the alkaline catalyst reduced the carbon
recovery of solid residue to less than 2%, revealing the benefits of
alkaline catalysts for SWE. Catalysts, especially alkaline catalyst,
increased the nitrogen recovery of biocrude at 240 °C and 280 °C.
This increase was accompanied by a decrease in nitrogen recovery
of solid residue at both temperatures. Gai et al. [37] carried out the
SWE of C. pyrenoidosa and reported that high temperatures, high
total solid ratio, and moderate retention time contribute to higher
carbon recovery of the biocrude. On the contrary, a low nitrogen
recovery could be obtained at low temperatures, low total solid
ratios, and long residence times. The authors also stated an impor-
tant foremost step in selecting the residence time to achieve bio-
crude with higher carbon and lower nitrogen recoveries. Chen
et al. [32] investigated mixed-culture algal biomass (25%)
co-liquefied with swine manure (75%). The crude fat in swine man-
ure increased the nitrogen recovery due to its reactions with fatty
acid derivatives, but the carbon recovery did not increase. These
authors also inferred that the recoveries may differ with varying
combinations of feedstock. Nitrogen recovery in the biocrude can
be reduced by promoting deamination of proteins prior to SWE
[60]. SWE in large-scale continuous flow reactors resulted in
824 S. Thiruvenkadam et al. / Applied Energy 154 (2015) 815–828
fouling and slagging due to the presence of alkali metals [45].
Aluminum, copper, iron, calcium, magnesium, potassium, sodium,
manganese, nickel, sodium, and zinc were detected during metallic
analysis of biocrude from Tetraselmis sp. [45]. The presence of met-
als such as Cu, Fe, Mn, Cr, Zn and Mo have been reported as catalyst
poisons during biocrude upgrading for denitrogenation and desul-
furization [45].
3.3. Modeling and LCA analysis
Johnson and Tester [43] developed a model for triglyceride
hydrolysis of two microalgae strains, Isochrysis sp. and
Thalassiosira weissflogii, operated at 250–350 °C in a batch reactor.
They tested the model on saturated fatty acids and then to unsat-
urated fatty acids. The total hydrolysis process comprised of three
sequential reversible reactions converting triglycerides, diglyc-
erides and monoglycerides, respectively, to diglycerides, mono-
glycerides and glycerol. A free fatty acid is released in each
reaction step on hydrolysis of water molecule with one ester bond.
Valdez et al. [68] conducted a useful kinetic modeling, including
the biochemical content of the microalgae for SWE. In the model,
the decomposition of algal biomacromolecules such as proteins,
carbohydrates and lipids were described by six rate constants.
Analysis of the rate constants showed that lipid decomposition rate
was exceeding that of protein decomposition. This explains that
lipids decomposition conditions are adequate for the decomposi-
tion of proteins. The authors also stated that SWE conditions for
lipid conversion will also enhance protein conversion to biocrude
with high N/C ratio, which would reduce the biocrude quality.
This model also suggested that protein- and lipid-rich algal species
are better feedstock than carbohydrate-rich algae for biocrude for-
mation. Previously, the same group developed a kinetic model
specific for Nannochloropsis sp. [69]. This kinetic model was devel-
oped from a reaction network that interconnected all product frac-
tions from SWE, and the model suggested that a reaction time of
few minutes is enough to accomplish SWE.
Zhu et al. [67] devised a process simulation model of LEA bio-
mass subjected to SWE and upgrading technologies such as
hydrotreating and hydrocracking. This model predicted the eco-
nomic benefits of large scale SWE plant. A techno-economic model
on SWE for algal biofuel production was developed by Delrue et al.
[70]. This model included elements such as continuous SWE, sepa-
ration and recovery of biocrude/bio-oil technologies, integrating
heat exchanger with SWE system, and a hydrotreating process to
upgrade biocrude. The sensitivity analysis of this model predicted
four important factors; biocrude yield, lower heating value (LHV)
of the produced biodiesel, CO2 aeration rate and heat recycling por-
tion. The authors reported that SWE yielded more biodiesel than
conventional lipid extraction pathway, regrettably with higher
GHG emissions. Moreover, the authors also preferred SWE over
anaerobic digestion for recovering energy from defatted biomass
residue. Venteris et al. [71] compared the biomass and nutrient
demands of lipid extraction (LE) and SWE under five different sce-
narios: Fuel and co-products yields from LE (Scenario 1) or SWE
(Scenario 2), LE with post algal extract recycled via anaerobic
digestion (Scenario 3) or Catalytic Hydrothermal Gasification
(CHG) (Scenario 4), and SWE followed by post algal residue treat-
ment with CHG (Scenario 5). On the basis of production levels,
the most efficient pathway was scenario 5 (SWE + CHG), though
with a trade-off in increased N consumption.
Life cycle assessment (LCA) studies reflect the possible environ-
mental concerns of this technique. LCA and techno-economic stud-
ies on algal biofuel systems have been published by Rickman et al.
[72]. The group developed a Utility-Connected Algae System
(UCAS) with a modular approach consisting of parameters such
as total pond area, flue gas pumping rate, and flue gas CO2
concentration and uptake efficiency. In this study, a significant
mitigation of CO2 emissions was difficult due to the complexity
of the parameters. LCA analysis by Fortier et al. [73] illustrated
the benefits of combining nutrient recycling and SWE, where the
algae could be cultivated at associated wastewater treatment
plants (WWTPs). Operating SWE reactors at a WWTP site is feasible
as the methane generated from anaerobic digestion can be used as
the heat source for SWE process. SWE at WWTPs results in lower
life-cycle greenhouse gas (LC-GHG) emissions than SWE taking
place at a petroleum refineries and this lower LC-GHG emissions
from WWTP/SWE pathway are the consequence of cutting logistics
spending on transporting algae from WWTP to petroleum refinery.
3.4. Biocrude upgrading
Algal oil generated directly after extraction contains impurities,
such as metals and heteroatom-containing substituents, which
might adversely affect the direct usage of the oil for biofuel pro-
duction. Bio-oils from SWE are of low quality and can be upgraded
by various strategies namely: (i) hydrotreating; (ii) hydrocracking;
(iii) supercritical fluids; (iv) solvent addition/esterification; (v)
emulsification; and (vi) steam reforming [74]. Prior to SWE, the
algae should be washed with distilled water to remove any water
soluble inorganic matter present with the algae species. Although
SWE is applied on wet biomass, the requirement for washing with
distilled water is dependent on the intended use of the extract.
Washing with distilled water only enhances the purity of the
extracts and does not affect the efficiency of SWE. For a generic
SWE, intensive culture dewatering is unnecessary compared to
other extraction approaches such as solvent extraction. The pri-
mary product of SWE for biodiesel production is biocrude or
bio-oil. The biocrude is then transesterified to biodiesel by the
addition of alcohol catalyzed by an acid or base catalyst. The estab-
lished method for biodiesel production from algae is a two-step
process: (i) extraction of bio-oil from algae and (ii) conversion of
bio-oil to biodiesel [75]. However, it is still a challenge to maximize
biodiesel production from algae as algal lipids contain high
amounts of unsaturated fatty acids. FAME resulting from transes-
terification of unsaturated fatty acids has an increased inclination
toward oxidation reaction, consequently deteriorating the biodie-
sel production process. This problem can be eliminated by hydro-
genating the double bonds of unsaturated fatty acids with the
help of hydrogenating catalysts. A high concentration of carbohy-
drates in algae is undesirable as it primarily results in biochar for-
mation [46]. Garcia-Alba et al. [44] reported that high-protein
algae species such as Spirulina contain high nitrogen content in
the biocrude and thus denitrogenation is necessary in terms of
oil upgrading steps. Direct infusion Fourier Transform Ion
Cyclotron Resonance Mass Spectrometry (FT-ICR MS) analysis of
bio-oil fractions of N. salina showed the presence of numerous
nitrogen heterocyclic and oxygenated compounds [4]. High nitro-
gen content has a detrimental effect on biocrude quality as it
results in NOX emissions during combustion [44]. Similarly, bio-
crude with high oxygen and sulfur contents are also prohibitive
[11,65]. The maximum permitted levels of sulfur and phosphorous
in biodiesel are respectively 15 ppm and 10 mg/kg as per US ASTM
D6751 standards [76]. The presence of polar compounds in bio-
crudes leads to corrosion and chemical instability after storage
[4]. Studies have been conducted on oil upgrading techniques such
as hydrodenitrogenation, hydrodeoxygenation and hydrocracking.
During nitrogen removal, harsh treatment conditions are recom-
mended since basic nitrogen compounds tend to deactivate the
catalysts by adsorbing to their active sites [29].
As mentioned previously, fresh bio-oil from algal biomass con-
tains high nitrogen and oxygen contents, deteriorating its quality.
With the intention of decreasing those contents, Cheng et al. [60]
 S. Thiruvenkadam et al. / Applied Energy 154 (2015) 815–828
demonstrated a biodiesel and biocrude co-generation process. In
this work, high-grade biodiesel was obtained from transesterifica-
tion of algal lipids via microwave irradiation. The algal residue was
processed for SWE to produce low-grade biocrude from the algal
carbohydrates and proteins. Comparison of the co-generation pro-
cess with direct SWE of raw microalgae delivered the following
results: (1) The conversion of lipids were effective in both pro-
cesses, (2) The partially hydrolyzed proteins in the transesterifica-
tion step of the co-generation process inhibited the reaction of
fatty acids with nitrogen-rich organics to yield long-chain nitrogen
compounds and thus reducing nitrogen content in the final bio-
crude, (3) Initial deamination of proteins in the cogeneration pro-
cess enhanced the formation of liquid fuels from carbohydrates,
preventing gas product which was observed in direct SWE of algal
biomass. However, compared to direct SWE, the co-generation pro-
cess increased oxygen content slightly from 14.02% to 15.86%,
while the nitrogen content decreased from 27.06% to 16.02% [60].
An interesting alternative proposed by Miao et al. [77] was aimed
at the removal of proteins and polysaccharides from the feedstock
before SWE treatment. The process is named as sequential
hydrothermal fractionation, where proteins and polysaccharides
are isolated from the feedstock at low temperature followed by
high temperature SWE for biocrude formation from the extracted
biomass. Complete in-depth information on individual compo-
nents present in the biocrude is particularly necessary for optimiz-
ing the SWE and its upgrading process [4].
Researchers have explored ways to tackle these downstream
processes. Roussis et al. [78] demonstrated a thermal treatment
process to remove oxygen and metals from fresh algal oils. They
found that the thermal treatment improves oil fluidity characteris-
tics by increasing volatility and decreasing viscosity thus reducing
their boiling point. This is advantageous to further downstream
processing steps, minimal poisoning effects and improved flow
properties. Bai et al. [79] examined the catalytic treatment of pre-
treated algal oil from SWE of C. pyrenoidosa. Different catalysts
were used: Activated carbon, Alumina, CoMo/c-Al2O3 (sulfided),
HZSM-5, Mo2C, MoS2, Ni/SiO2–Al2O3, Pd/C, Pt/C, Pt/C (sulfided),
Raney-Ni and Ru/C. In these experiments, the algal biocrude after
SWE was pretreated at 350 °C for 4 h, repeatedly for four times,
before the upgrading process. Amongst the catalysts investigated,
Ru/C catalyst produced the highest upgraded bio-oil yield (68.5%)
followed by Ni/SiO2–Al2O3 (68.2%). All the catalysts tested showed
denitrogenation activity, while only Pt/C, Ru/C, alumina, HZSM-5,
and Raney-Ni promoted deoxygenation activity. Higher C content
and HHV were observed for the catalyzed-upgraded bio-oil com-
pared to the uncatalyzed bio-oil. Deoxygenation and denitrogena-
tion processes were executed best by Ru/C and Raney-Ni
respectively. The combination of Ru/C and Raney-Ni showed a pos-
itive effect in terms of yield, C and H contents, and HHV of the
upgraded bio-oil. A two-step upgrading process, described by
Zhang et al. [52], involved SWE at a low temperature of 260 °C
for 60 min in H2 followed by upgrading SWE filtrates in supercrit-
ical ethanol at 300 °C for 60 min in H2. Unfortunately, this two-step
process did not provide significant results when compared with
SWE at 300 °C for 30 min in H2.
3.5. Scale-up implications and recent developments
Batch experiments of SWE have provided insights into biofuel
production from algal feedstock [37,45,60,61]. In spite of this
increased interest, commercial and continuous SWE are still under
investigation and development. A research group from Australia
[26] focused on the development of continuous pilot scale SWE
reactors and achieved a maximum biocrude yield of 41.7% from
Chlorella sp. processed at 350 °C and 3 min residence time.
Though higher yields were achieved at higher SWE reaction
825
temperatures with reduced oxygen content, an increase in nitrogen
content was observed at high temperatures; hence the quality of
the biocrude was compromised. Low-lipid algal species are consid-
ered to be favorable feedstock for SWE process [32]. With difficul-
ties pertaining to culturing pure-monocultures, some researchers
have proposed integrating algal cultivation with wastewater sys-
tems, resulting in a positive net energy balance [29,32]. Recently,
co-liquefaction of swine manure (SW) and mixed-culture wastew-
ater algae (AW) was explored by Chen et al. [32]. Co-liquefaction of
25% AW and 75% SW gave the highest biocrude yield (35.7%) under
the experimental conditions employed. High ash content of about
47.5% in AW harvested from full-scale mixed algal wastewater
treatment plant was found to block biocrude formation. The dilu-
tion of total ash contents in the combined feedstock with 75%
SW improved biocrude yield. For other combinations, high ash
contents of the feedstock resulted in the formation of aqueous or
solid products. The saponification of ash contents result in aqueous
products. Direct deoxy-liquefaction, a modified SWE process, was
first explored by Li et al. [61] and this liquefaction aims to produce
biocrude with lower oxygen content. Macroalga Gelidium amansii
was tested for deoxy-liquefaction at 350 °C and it produced
11.98% oil with 7.30% oxygen, which was very much lower than
those found in the raw material (64.48% oxygen). The presence of
nitrogen compounds in the bio-oil leads to serious environmental
concerns, and these nitrogen compounds are derived from protein
and polysaccharide fractions. Thus, a two-step SWE process named
as Sequential SWE (SEQSWE) has been developed with the aim of
reducing obnoxious nitrogen compounds in bio-oil by removing
proteins and polysaccharides at low temperature as a first step of
SEQSWE, followed by SWE of extracted biomass to produce
bio-oil [77].
4. Other products
4.1. Aqueous product
The aqueous phase product from SWE contains carbon and
nitrogen with negligible amounts of hydrogen and carbon monox-
ide [33]. Alkaline catalyst (Na2CO3) increased the carbon recovery
of the aqueous phase from SWE of C. pyrenoidosa to 52.1%, which
is higher than the value obtained from non-catalyzed SWE tests
at 240 °C (32.0%) [57]. This study also implied that the aqueous
product gets promoted with the help of alkaline catalysts during
SWE. High-carbon aqueous phase can be recycled as a substrate
for the growth of mixotrophic organisms [26]. Biller et al. [62]
tested the feasibility of using the aqueous phase for microalgae
cultivation. After filtering the aqueous product, the filtrate was
diluted prior to microalgae cultivation in order to reduce extreme
concentrations of nutrients present in the aqueous phase.
Microalgal growth profile can be optimized by selecting the right
dilution of SWE aqueous product. A report by Johnson et al. [80]
studied the effect of nutrient production on algae LCA, considering
all energy and materials inputs. This study reported the signifi-
cance of nutrient contributions to algae biofuel production.
Fertilizer production and dewatering process are among the most
endoergic steps during algal-to-biofuel pathway and a potential
solution is the recycling of aqueous water for biomass synthesis
combined with the SWE process [73]. Orfield et al. [81] have
reported that the recovery and recycling of aqueous product
improve the life cycle performance of algal biorefinery. The authors
explored two different pathways in recycling the aqueous product:
(i) CHG of the aqueous products and (ii) cultivation of the bac-
terium Escherichia coli on the aqueous products. The flue gas pro-
duced from CHG is directed to a hydrogen production plant
which produces hydrogen gas for hydrotreating. The bacterial
826 S. Thiruvenkadam et al. / Applied Energy 154 (2015) 815–828

growth on the aqueous products increased the carbon footprint is CO2, formed via steam reforming or water-gas shift reactions.
and reduced the energy return on investment (EROI). EROI is an Other gases include H2, CO, CH4 and C2H6 [5,48]. High tempera-
important metric that facilitates the quantification of environmen- tures [45] and longer residence times result in gas formation
tal performance of a biofuel together with economic viability [82]. [36,38]. At elevated temperatures, partial decomposition of bio-
crude leads to gas production [61] and also increases the carbon
4.2. Solid residue recovery of gas products [57]. Interestingly, a denser feedstock
medium with a low biomass to water ratio decreases gas yields
Another product from SWE is solid residue, which includes a due to enhanced extraction of biocrude oils [37,38]. A similar trend
high concentration of ash and low concentrations of hydrogen, was observed for increasing acetone/biomass ratio from 10:2.5 to
nitrogen and sulfur [1]. The distribution of products from SWE of 16:2.5 (mL/g) [48]. Bai et al. [79] reported that most catalyzed
algae can be seen in Table 3. The solid yields vary according to reactions, except those involving Ru/C catalyst, have no effect on
the feedstock characterization. For example, algal species with gas formation, explaining that gas formation is a thermal process.
high inorganic contents yield more solid residue. It has been High gas yields from Ru/C could be suppressed by combining it
reported that the solid yield decreases with increasing tempera- with Raney-Ni catalyst because the combination of these two cat-
ture [38]. The solid residues can be used as asphalt [36] and/or fer- alysts showed good deoxygenation and denitrogenation of the bio-
tilizer [11] if N partitions into the solid phase during the SWE crude oils. Pt/C catalyst was also seen to promote the formation of
process. FTIR spectra of solid residue from SWE of Ulva fasciata methane and ethane gases, generated from cracking reactions [5].
were presented by Singh et al. [63]. The macroalga carbohydrates Gas products rich in CO2 are potentially beneficial and these prod-
and proteins were indicated by O–H and N–H bonds observed from ucts can be recycled back to algae ponds or could be utilized for
broad bands around 3406 cm 1. Peaks found at 1451 cm 1 and heat generation and/or power.
1103 cm 1 represented C–O stretching vibrations belonging to sec-
ondary and primary alcohols of the carbohydrates respectively. The 5. Conclusion
decomposition of proteins and carbohydrates during SWE were
confirmed by the absence of relevant peaks in SWE-treated solid Advances in SWE have led to massive interests in the conver-
residue compared to that of the raw macroalga U. fasciata. It was sion of algae to transportation fuels via SWE. This low-cost and
also observed that the solid residue yields were lower for alkaline eco-friendly technology could in principle be used for production
catalyzed SWE than heterogeneous catalyzed SWE at 240 °C [57]. of bio-products and biofuels from algae and other biomasses.
The carbon recovery of the solid residue increased when a This is appreciated as a substantive effort to the contribution of
mixed-culture algal biomass (25%) was co-liquefied with swine biofuels in the future bioenergy sector. In a closed loop system,
manure (75%) in a SWE process. This was due to the presence of algae production costs could be reduced by few approaches, such
hemicellulose [32]. as recycling nutrient-rich aqueous products into the cultivation
system, utilizing co-products, and implementing heat integration
4.3. Gas product system. The use of heterogeneous catalysts has shown to produce
high quality bio-oil but requires some improvements to minimize
Gaseous products are released from SWE reactors significantly, the effect of fouling and catalyst deactivation. The road to commer-
and in many cases, the yield of gases are calculated on difference cialization will mainly be associated with energy demands to avoid
basis [10,61]. The most abundant gas product in most SWE studies the production of biofuel with higher greenhouse gas emissions
than conventional fuel. For full-scale application, pilot studies
Table 3 should be focused on addressing the present technological prob-
SWE yields from specific product phases for different algae species. lems associated with product yield and composition. Beyond tech-
Feedstock Biocrudea Solidsa Aqueousa Gasa Reference nological problems, algae cultivation systems also play a key role
Freshwater algae in improving this technology. Additional research and develop-
Chlorella vulgaris 40 2 54 4 [49] ment studies are necessary to thoroughly design and identify the
Cladophora vagabunda 19.7 18.7 61.7b [46] realistic potential of this technology for production of biofuels.
Desmodesmus sp. 46.5 9.1 17.8 22.3 [44]
Nannochloropsis gaditana 34.4 24.7 36.2 6.7 [65]
Oedogonium sp. 26.2 10.2 63.6b [46] Acknowledgements
Phaeodactylum tricornutum 40.8 17.8 22.9 12.5 [65]
Scenedesmus obliquus 17.6 41.6 27.1 6.1 [65] This work has been supported by Fundamental Research Grant
Spirulina sp. 34 2 14 50 [49] Scheme (Project Code: 03-02-13-1297FR) and the Department of
Marine algae Chemical and Environmental Engineering, Universiti Putra
Chaetomorpha linum 9.7 8.4 82.0b [46]
Malaysia.
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