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Applied Energy
journal homepage: www.elsevier.com/locate/apenergy
Department of Chemical and Environmental Engineering, Universiti Putra Malaysia, 43400 Serdang, Malaysia
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
Article history:
Received 20 November 2014
Received in revised form 19 May 2015
Accepted 21 May 2015
Available online 7 June 2015
Keywords:
Subcritical water extraction
Algae
Biocrude
Bio-oil
Biofuels
Thermochemical
a b s t r a c t
Algal biomass is appreciated as an essential bioenergy feedstock owing to the rapid growth rate of algal
cells and the capacity to harbor substantial quantities of biochemicals via CO2 biosequestration for
biofuel production. Amongst the various thermochemical technologies for converting algal biomass to
biofuels, Subcritical Water Extraction (SWE) demonstrates signicant capacity for generating liquid
transportation fuels from algae with minimal environmental impacts. The SWE process expends pressurized water to produce biocrude or bio-oil as well as aqueous, solid, or gaseous by-products. However, the
existence of high levels of heteroatoms in biocrude hinders its application in internal combustion
engines, and this has triggered studies into parametric characterization of biocrude production from algal
biomass. This article comprehensively reviews the process principles, optimal conditions, engineering
scale-up and products development to ascertain the viability of an industrial-scale SWE process for
biofuel production from algae.
2015 Elsevier Ltd. All rights reserved.
Contents
1.
2.
3.
Introduction . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
The theory of SWE . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
Biocrude . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
3.1.
Factors affecting biocrude yield . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
3.1.1.
Effect of temperature . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
3.1.2.
Effect of residence time . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
3.1.3.
Effect of water density and biomass loading . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
3.1.4.
Effect of other solvent/co-solvents . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
3.1.5.
Effect of catalyst . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
3.1.6.
Effect of heating rate and stirring . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
3.1.7.
Effect of algae strain. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
3.2.
Energy recovery. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
3.3.
Modeling and LCA analysis . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
3.4.
Biocrude upgrading . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
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/ 2015 Elsevier Ltd. All rights reserved.
816
816
817
817
817
819
820
820
820
821
822
822
824
824
816
4.
5.
3.5.
Scale-up implications and recent developments . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
Other products . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
4.1.
Aqueous product . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
4.2.
Solid residue . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
4.3.
Gas product . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
Conclusion . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
Acknowledgements . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
References . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
1. Introduction
Climate change, increasing energy consumption, growing
human population and the development of new economies call
for the creation of new and sustainable energy technologies such
as biofuels [1]. The development of rst and second generation biofuels from proposed candidates, such as energy crops, lignocellulosic biomass, and agricultural wastes carry many demerits from
a biodiversity and economic perspective [2]. In recent years, there
has been an increasing interest in algal biofuels, so-called third
generation biofuels. Algae are a unique biomass feedstock for sustainable production of biofuels. Algae, one of the fastest growing
photosynthetic organisms on earth, have biomass productivity
rates higher than terrestrial plants [3]. They have several advantages including tolerance to extreme environmental conditions,
eco-friendly cultivation process, simple life cycle and resource
availability for large-scale production [25]. Additional benets
of algae over food crops include fast growth rates, less water
intake, adaptation to various water sources (fresh, seawater,
saline/brackish and wastewater), high photosynthetic efciency,
carbon dioxide (CO2) biosequestration, phytoremediation, inexpensive cultivation techniques using non-arable land and short
harvesting periods. Notwithstanding these benets, algal biofuel
development faces a few drawbacks which include low biomass
densities and high operating costs for biomass generation and conversion [6]. Although algal based biofuels generate approximately
13% CO2 lower emissions from combustion relative to CO2 emissions from petroleum diesel [7], in terms of absolute emission
levels, algal biofuels can be signicantly high for full-scale applications. The development of biofuels from algal biomass has been
signicantly successful under lab-scale conditions. However,
opportunities for commercial-scale applications should focus on
addressing related environmental, technological and economic
drawbacks [2]. A wide variety of bioactive materials for pharmaceutical, 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 bers, have been realized from algae.
Most existing technologies for production of algal biofuels primarily aim on extracting lipids from algae and these technologies
involve downstream harvesting or dewatering processes such as,
occulation 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 gasication,
pyrolysis and FischerTropsch process, require dry biomass and
operational temperatures higher than 600 C [9]. Cost-effective
and energy-effective strategies play a key role in commercialization 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 (530%), with no requirement of energy-intensive culture 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
825
825
825
826
826
826
826
826
817
818
phase and solid residue yields [44]. Eboibi et al. [45] examined
the effect of temperature on SWE of Tetraselmis species.
Increasing the reaction temperature from 330 C to 350 C for
5 min increased the biocrude yield. However, increasing the
819
Fig. 3. A schematic drawing of a typical batch scale SWE process. Source: Li et al. [14]; reprinted with permission.
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 decreasing trend in biocrude yield was observed with increasing temperature. 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 products [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 respectively. 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 benecial 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, generates 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 retention times do not affect the lipid extraction recovery from algal biomass [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
821
Table 1
Summary of elemental compositions and caloric values of fresh algae and biocrudes produced from catalyzed SWE processes.
Algae
Feedstock
Biocrude
Elemental Compositiona
a
b
c
d
e
f
g
h
HHVb
Catalyst: Na2CO3
Chlorella vulgaris
Dunaliella tertiolecta
Nannochloropsis oculata
Porphyridium cruentum
Spirulina sp.
52.6
39f
57.8
51.3
55.7
7.1
5.37f
8
7.6
6.8
8.2
1.99f
8.6
8
11.2
32.2g
53.02f,g
25.7g
33.1g
26.4g
0.5
ND
NA
NA
0.8
Catalyst: HCOOH
Chlorella vulgaris
Chlorella vulgaris
Nannochloropsis oculata
Porphyridium cruentum
Spirulina sp.
Spirulina sp.
53.6
52.6
57.8
51.3
55.7
54.4
7.3
7.1
8
7.6
6.8
7.6
9.2
8.2
8.6
8
11.2
10.9
29.4g
32.2g
25.7g
33.1g
26.4g
26.3g
Catalyst: CH3COOH
Chlorella vulgaris
Spirulina sp.
53.6
54.4
7.3
7.6
9.2
10.9
Catalyst: KOH
Chlorella vulgaris
Spirulina sp.
53.6
54.4
7.3
7.6
Catalyst: Pt/Al2O3
Chlorella vulgaris
Nannochloropsis occulta
52.6
57.8
Catalyst: Ni/Al2O3
Chlorella vulgaris
Nannochloropsis occulta
SWE
conditions
Elemental Compositiona
HHVb
Yieldc
Tempd
Timee
Reference
23.2
20.08
17.9
14.7
21.2
73.6
63.55f
69.6
46.1
75.4
10.7
7.66f
9.2
5.6
10.8
4.9
3.71f
3.8
3.2
4.6
10.7g
25.08f,g
17.3g
13.3g
8.7
0
ND
0
0.2
0.5
37.1
30.74
35.5
22.8
34.8
30
25.8
28
30
18
350
360
350
350
350
60
5
60
60
60
[49]
[24]
[49]
[49]
[49]
0.5
0.5
NA
NA
0.8
0.83
23.2
23.2
17.9
14.7
21.2
21.2
72.1
70.8
74.7
72.5
72.7
72.7
9.5
9.4
10.6
9.1
9.8
9.8
6.4
5.3
4.3
5.7
5.7
5.7
11.5g
13.9g
10.4g
13.3g
10.9g
10.9g
0.5
0.6
0
0.4
1
1
35
33.2
39
36.3
35.1
35.6
22h
30
28
20
22
14.2h
300
350
350
350
350
350
60
60
60
60
60
60
[53]
[49]
[49]
[49]
[49]
[53]
29.4g
26.3g
0.5
0.83
23.2
21.2
70.8
71.7
9.4
9.7
5.3
6.1
14.1g
11.6g
0.4
0.9
34.2
35.1
23h
16.6h
300
350
60
60
[53]
[53]
9.2
10.9
29.4g
26.3g
0.5
0.83
23.2
21.2
74
74.6
12.9
11.4
4.3
5.1
8.9g
8.5g
0.2
0.5
39.9
33.4
22.4h
15.2h
350
350
60
60
[53]
[53]
7.1
8
8.2
8.6
32.3g
25.7g
0.5
ND
23.3
17.9
74.8
74
9.7
10.2
5.6
3.6
9.3g
12g
0.6
0.1
37.9
38.2
38.9h
30.2h
350
350
60
60
[49]
[49]
52.6
57.8
7.1
8
8.2
8.6
32.3g
25.7g
0.5
ND
23.3
17.9
75.4
76.8
6.7
9.4
5.4
3.6
12.6g
10.2g
0
0
34.5
38.2
30.0h
18.1h
350
350
60
60
[49]
[49]
Catalyst: Co/Al2O3
Chlorella vulgaris
Nannochloropsis occulta
52.6
57.8
7.1
8
8.2
8.6
32.3g
25.7g
0.5
ND
23.3
17.9
75.2
77
8.3
8.9
5.7
4.6
10.7g
9.4g
0
0
36.2
37.6
38.7h
25.5h
350
350
60
60
[49]
[49]
Catalyst: NiMo/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]
822
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 respectively. They also concluded that higher heating rates are more
favorable in enhancing biocrude yield than the utilization of catalysts. The benecial effects of rapid heating [10] are: (i) accelerating 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 transesterication [31]. The
authors also conrmed that biomass stirring at lower temperatures
provided better results with simultaneous extraction and transesterication of wet microalgal biomass.
lipid
protein
carbohydrate
60
80
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
100
120
823
Feedstock
Biocrude
Elemental Compositiona
Chaetomorpha linum
Chlorella sp.
Chlorella sp.
Chlorella vulgaris
Chlorella vulgaris
Chlorella vulgaris
Cladophora coelothrix
Cladophora vagabunda
Derbesia tenuissima
Desmodesmus sp.
Dunaliella tertiolecta
Gelidium amansii
Laminaria saccharina
Laminaria saccharina
Mixed culture algae
Nannochloropsis gaditana
Nannochloropsis occulta
Nannochloropsis oceanica
Nannochloropsis oculata
Nannochloropsis salina
Nannochloropsis salina
Nannochloropsis sp.
Oedogonium sp.
Phaeodactylum tricornutum
Porphyridium cruentum
Porphyridium purpureum
Scenedesmus almeriensis
Scenedesmus obliquus
Spirulina sp.
Spirulina sp.
Spirulina platensis
Tetraselmis sp.
Tetraselmis suecica
Ulva ohnoi
a
b
c
d
e
f
g
h
HHVb
26.5
53.5f
60.5
42.3
52.6f
52.6f
30.9
37.5
29.2
51.96f
51.9
28.04
39.44f
31.3
27.9
51
57.8f
50.06
57.8f
55.16
56.52
43.7
36.6
38
51.3f
45.6
50.6
44.4
53.7f
55.7f
42.26
42
45
27.7
4.1
7.4f
9.1
5.1
7.1f
7.1f
5
5.9
4.8
7.31f
7.5
4.85
5.14f
3.7
3.01
6.6
8f
7.46
8f
6.87
8.28
7.7
5.7
4.8
7.6f
6.1
6.4
5.4
7.7f
6.8f
5.86
6.8
5.9
5.5
3.4
11f
1.9
6.2
8.2f
8.2f
5.2
6.5
4.5
6.86f
8.6
2.62
2.99f
2.4
3.9
6.9
8.6f
7.54
8.6f
2.73
8.51
7.5
4.8
5.2
8f
6
6.8
5.8
12.1f
11.2f
3.47
8
6.3
3.5
31
27.6f,g
21.8
2.1
0.5f
32.2f,g
32.3f,g
34.9
32.9
27.4
33.87f,g
0.4
0.5f
0.5f
2.3
1.8
2.8
10.3
24.3
32.3
23.2
23.2
12.7
16.4
12.4
23.44
0.5
64.48g
52.03f
26.3
65.2g
25.7f,g
34.47g
25.7f,g
33.97g
26.69g
29.1
30.9
33.1f,g
25.9f,g
26.4f,g
47.26g
40.2g
41.4
0.6f
0.7
0.4
0.4
ND
0.47
NA
1.27
0.4
0.7
NA
1.1
0.4
0.3
0.6
0.8
1.15
3
1.1
5
9.8
14.46
12
12.9
17.9
21.46
17.9
25.4
24.17
22.4
15.8
14.7
24.9
21.2
20.4
19.2
11.7
SWE
conditions
Elemental Compositiona
C
70.9
70.7f
75.6
70.6
70.7f
70.7f
71.6
71.1
73
75.8f
71.3
78.46
75.54f
82
59.4
71.5
68.1f
72.58
68.1f
77.2
72.59
74
72.1
62.9
72.8f
69.1
72.6
69.3
68.3f
73.3f
70.69
71
62.6
72.6
7.7
8.8f
12
9.2
8.6f
8.6f
8
8.3
7.5
9.1f
9.1
10.24
9.16f
7.1
7.79
9.7
8.8f
9.75
8.8f
9.01
9.79
10.2
8.1
8
8.5f
8.4
9.4
9.1
8.3f
9.2f
8.05
9.5
7.4
8.2
6.8
7.7f
0.3
5.5
5.9f
5.9f
7.1
6.8
6.5
6f
5.3
4
3.65f
4.9
2.50
3.7
4.1f
5.09
4.1f
2.75
5.2
5.4
6.3
4.7
5.4f
5
4.1
5.1
6.9f
7f
7.22
5
4.8
5.8
11.4
12.0f,g
11.5
12.3
14.8f,g
14.8f,g
10.6
10.6
10.6
9.1f
12.2
7.3g
11.66f
5.4g
30.3 g
11.5
19f,g
12.06g
18.9f,g
8.71
12.42g
9.5
10.4
12
13.3f,g
15.2
12.5
12.9
15.4f,g
10.4f,g
10.06
14g
14
11
0.1
0.8f
0.4
0
0
0.9
1.3
0.7
0.4
0.62f
0.2
0
0.52
0
1
0.8
0.3
0.4f
0.5
0.3
0.2
1.1f
1f
0.77
0.6
0.4
0.4
HHVb
Yieldc
Tempd
Timee
32.5
33.8
34.2
34.4
35.1
35.1
33.3
33.5
33.2
36.6
34.6
40
35.97
36.5
25.8
35.4
34.5
36.35
34.5
38.1
36.3
31.5
33.7
30.3
35.7
32.7
35.3
33.8
32
36.8
34.3
35
29.3
33.8
9.7
41.7
82.9
33
40
35.8h
13.5
19.7
19.7
46.5
44.8
11.98
79h
19.3
330
350
220
250
350
350
330
330
330
350
250
350
350
350
300
250
350
300
350
350
340
260
330
250
350
250
250
250
300
350
350
350
250
330
5
3
90
5
60
60
5
5
5
60
5
20
15
15
60
5
60
30
60
30
30
60
5
5
60
5
5
5
5
60
30
5
5
5
34.4
34.3h
40.08
38
55.6
55.0
26.2
40.8
22
24.7
35.7
17.6
34
65
29.4
18.7
Reference
[46]
[26]
[66]
[65]
[49]
[56]
[46]
[46]
[46]
[44]
[65]
[61]
[10]
[39]
[32]
[65]
[56]
[60]
[49]
[54]
[14]
[66]
[46]
[65]
[49]
[65]
[65]
[65]
[26]
[49]
[54]
[45]
[65]
[46]
C. linum were 55.7%, 54%, 52.5%, 40.1%, 35.3% and 30.6% respectively [46]. Energy recoveries of 3887% and 52.5% were obtained
from biocrudes of Tetraselmis sp. [45] and mixed-culture algal biomass [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 biocrude from S. platensis co-liqueed 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 6388% and 2453% for carbon
and nitrogen recovery respectively in the biocrude from SWE of
Tetraselmis species. Low nitrogen recovery (8.4116.8%) 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 heterogeneous 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
824
825
4. Other products
4.1. Aqueous product
The aqueous phase product from SWE contains carbon and
nitrogen with negligible amounts of hydrogen and carbon monoxide [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 ltering the aqueous product, the ltrate was
diluted prior to microalgae cultivation in order to reduce extreme
concentrations of nutrients present in the aqueous phase.
Microalgal growth prole 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 signicance 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]. Oreld et al. [81] have
reported that the recovery and recycling of aqueous product
improve the life cycle performance of algal biorenery. The authors
explored two different pathways in recycling the aqueous product:
(i) CHG of the aqueous products and (ii) cultivation of the bacterium Escherichia coli on the aqueous products. The ue gas produced from CHG is directed to a hydrogen production plant
which produces hydrogen gas for hydrotreating. The bacterial
826
a
b
f
Feedstock
Reference
Freshwater algae
Chlorella vulgaris
Cladophora vagabunda
Desmodesmus sp.
Nannochloropsis gaditana
Oedogonium sp.
Phaeodactylum tricornutum
Scenedesmus obliquus
Spirulina sp.
40
19.7
46.5
34.4
26.2
40.8
17.6
34
2
18.7
9.1
24.7
10.2
17.8
41.6
2
54
61.7b
17.8
36.2
63.6b
22.9
27.1
14
[49]
[46]
[44]
[65]
[46]
[65]
[65]
[49]
Marine algae
Chaetomorpha linum
Chlorella vulgaris
Cladophora coelothrix
Derbesia tenuissima
Dunaliella tertiolecta
Gelidium amansii
Laminaria saccharina
Nannochloropsis oculata
Porphyridium cruentum
Porphyridium purpureum
Scenedesmus almeriensis
Tetraselmis sp.
Tetraselmis suecica
Ulva fasciata
Ulva ohnoi
9.7
33
13.5
19.7
44.8
11.98
79f
38
22
24.7
35.7
65
20.4
11
18.7
8.4
27
10.4
8.1
11.9
40.23
7f
2
4
27.6
36.6
13
21.1
24
12.1
82.0b
29.9
76.1b
72.2b
38.3
5f
58
74
34
17.5
14
28
69.2b
[46]
[65]
[46]
[46]
8.7
[65]
26.55 [61]
f
3
[10]
2
[49]
2
[49]
10.9 [65]
9.1
[65]
8
[45]
12.6 [65]
9
[63]
[46]
22.3
6.7
12.5
6.1
50
10.8
[36]
[37]
[38]
[39]
[40]
[41]
[42]
[43]
[44]
[45]
[46]
[47]
[48]
[49]
[50]
[51]
[52]
[53]
[54]
[55]
[56]
[57]
[58]
[59]
[60]
[61]
[62]
[63]
827
828
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