Fuel 285 (2021) 119106

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Full Length Article

Effect of reaction temperature on the conversion of algal biomass to bio-oil T

and biochar through pyrolysis and hydrothermal liquefaction
Kathirvel Brindhadevia, Susaimanickam Antob, Eldon R. Renec, Manigandan Sekard,
Thangavel Mathimanib, Nguyen Thuy Lan Chie, , Arivalagan Pugazhendhie
⁎

a
Institute of Research and Development, Duy Tan University, Da Nang 550000, Viet Nam
b
Department of Energy and Environment, National Institute of Technology, Tiruchirappalli 620015, Tamil Nadu, India
c
Department of Environmental Engineering and Water Technology, IHE Delft Institute for Water Education, Westvest 7, 2601DA Delft, the Netherlands
d
Department of Aeronautical Engineering, Sathyabama Institute of Science and Technology, Chennai, India
e
Innovative Green Product Synthesis and Renewable Environment Development Research Group, Faculty of Environment and Labour Safety, Ton Duc Thang University, Ho
Chi Minh City, Viet Nam

GRAPHICAL ABSTRACT

ARTICLE INFO ABSTRACT

Keywords: Thermochemical methods namely pyrolysis, gasification/hydrothermal gasification, combustion, hydrothermal

Algae liquefaction and hydrothermal carbonization are widely practiced to convert algal biomass into fuels. Among the
Hydrothermal liquefaction methods, pyrolysis, and hydrothermal liquefaction are most commonly practised to convert numerous algal
Pyrolysis biomasses into bio-oil and/or biochar to substitute crude oil in petroleum refinery. In this regard, this review is
Temperature
focused on the conversion of various microalgal; and cyanobacterial biomasses into bio-oil, and solid char
Bio-oil
products through pyrolysis and hydrothermal liquefaction. Initially, pyrolysis and hydrothermal liquefaction of
Biochar
Biofuel algal biomass on bio-oil and biochar yield have been reviewed. As the composition and yield of bio-oil from
algae depends on the reaction temperature, detailed account of the impact of temperature on the quantity and
quality of bio-oil and solid char obtained from pyrolysis and hydrothermal liquefaction were comprehensively
presented in the review. Eventually, this article provides opportunities and scope in the pyrolysis and hydro-
thermal liquefaction of algae for further research.

1. Introduction of conventional energy sources for industrialization and thus, the ex-
haustion of fossil fuels and emission of pollutants gases poses a decisive
The world is facing a massive energy crisis owing to the utilization moment of energy demand [1,2]. In this regard, biofuel is one of the

⁎
Corresponding author.
E-mail address: nguyenthuylanchi@tdtu.edu.vn (N. Thuy Lan Chi).

https://doi.org/10.1016/j.fuel.2020.119106
Received 21 April 2020; Received in revised form 2 August 2020; Accepted 24 August 2020
Available online 06 November 2020
0016-2361/ © 2020 Elsevier Ltd. All rights reserved.
K. Brindhadevi, et al.
Fig. 1. Schematic illustration of pyrolysis and HTL of algal biomass and their end products.
alternatives for renewable options to minimize the dependence on fossil
fuels and also to decrease the emission of greenhouse gases [3,4].
Worldwide, substantial development in biofuel production sectors, i.e.
biorefineries, have been witnessed that prompt the concerns over their
governance and environmental impacts [5]. Biofuel produced from
‘first’ generation feedstocks’ has showed several issues such as inter alia
high water consumption, water pollution, biodiversity loss, land use
and degradation, inconsistency in food price, ample pesticide and fer-
tilizer inputs [5]. To combat the above-said concerns, non-edible crops
based second-generation feedstocks have been ascertained, however,
they have also posed certain rudimental demerits like high land re-
quirement and seasonal variation of the feedstocks [6]. Under these
circumstances, harnessing the potential of algae as a third generation
feedstock for cutting down the fossil fuel usage, mitigating CO2 from
the atmosphere, are the current focal points in the commercial biofuel
production.
The term “Algae” is generic that encompasses a polyphyletic group
of unicellular (microalgae) and multicellular organisms (macroalgae)
[5]. Algae are the third-generation feedstock to produce biofuels
through biochemical, thermochemical and biological techniques [7].
Though biofuel from algae imparts various benefits, biofuel industry
will not reach its skyline unless the algal biofuel is sold at a low price or
at a price that is competitive with commercial grade gasoline. In this
perspective, the conversion of algal biomass into various fuels like bio-
oil or biochar or syngas is being experimented through thermochemical
conversion methods [8]. Microalgae are next generation potential
biomass as they are rich in carbohydrates, lipids and proteins compo-
nents [9]. Contrary to the conversion of lipid into biodiesel, the key
macromolecules of algae such as carbohydrate, protein, and lipid, are
apt for bio-oil production through pyrolysis, hydrothermal liquefaction
(HTL) and gasification techniques [10]. HTL is performed at the tem-
perature between 250 and 374 °C in water reaction medium and yields
bio-oil [11,12], pyrolysis and gasification requires 400–900 °C and
pyrolysis majorly produces solid char, and bio-oil, while gasification
produces gaseous products [10].
Among the thermochemical methods, pyrolysis and HTL produces
2
Fuel 285 (2021) 119106
bio-oil and biochar and it is influenced by the reaction temperature.
Thus, the purpose of this review was to succinctly review the tem-
perature influence on pyrolysis and HTL processes. Although there are
some literature on the mechanism of pyrolysis and HTL, a fairly de-
tailed knowledge of temperature influence on their respective product
yield is required to determine why the product yield may be better in
one process than another. Therefore this review article focused on the
discussion of how the difference in temperature affects the reaction
mechanism and the properties of the different products derived from
pyrolysis and HTL.
2. Pyrolysis
Pyrolysis, an emerging thermochemical technique, utilizes nu-
merous and different kinds of biomasses for char or bio-crude produc-
tion. Pyrolysis or dry pyrolysis is an endothermic reaction that de-
composes the biomass at extremely high temperature in the absence of
oxygen and under atmospheric pressure, resulting in solid (bio-char),
liquid (bio-oil) and gaseous (syngas) products [13,14]. Apart from the
conventional dry pyrolysis process, the pyrolysis technology can also be
carried out under subcritical or supercritical conditions. Under these
conditions water acts as the reaction medium at higher temperature and
pressure, usually above 374 °C and 22.1 MPa respectively. Pyrolysis, in
supercritical condition, is much favoured than subcritical condition
because of the following reasons: (i) water remains polar in subcritical
and non-polar in supercritical conditions, and (ii) dielectric constant of
water in supercritical condition is low. For these reasons, under su-
percritical condition water behaves as an excellent organic solvent and
aid in solubilizing the non-polar organic compounds [15,16]. At present
many technological developments in bio-oil production from several
consistent feedstock have emerged to replace the existing fossil fuels
[17]. Aquatic biomass have been well established as the consistent
feedstock for biomass conversion by pyrolysis owing to its properties
such as, (i) lack of complex polymers such as lignin, cellulose, hemi-
cellulose, etc, thereby facilitating the degradation at relatively low
temperatures, (ii) low O/C ratio leading to high calorific value, (iii) low
K. Brindhadevi, et al. Fuel 285 (2021) 119106

Table 1
Effect of temperature on the pyrolysis of different algal biomasses.
Microalgal strains Temperature (°C) Bio-oil yield (%) Atomic ratios of Bio-oil Biochar yield (%) References

Chlorella protothecoides 500 17.5 1.72 (H/C) – [30]

0.24 (O/C)
Microcystis aeruginosa 500 23.7 1.71 (H/C) – [30]
0.27 (O/C)
Chlorella protothecoides 500 52 – – [74]
Spirulina platensis 500 28.5 1.68 (H/C) 57.29 as Fixed carbon (FC) [27]
0.06 (O/C)
Chlorella protothecoides 450 57.9 – – [75]
Chlorella vulgaris 400 72 – ∼22 [76]
Chlorella vulgaris 500 53 – 31 [31]
Isochrysis sp. 475 41.32 – – [77]
Tetraselmis sp. 500 25.86 1.56 (H/C) ∼18 [18]
0.15 (O/C)
Isochrysis sp. 500 25.49 1.55 (H/C) ∼25 [18]
0.09 (O/C)
Pavlova sp. 500 23.2 – ∼34 [43]
Spirulina sp. 550 45 – ∼31 [17]
Scenedesmus dimorphus 500 39.6 1.49 (H/C) ∼27 [78]
0.08 (O/C)
Isochrysis sp. 475 49.36 – – [79]
Scenedesmus sp. 480 55 – 15.9 as FC [80]
Microcystis sp. 500 59 0.34 (O/C) 25.6 [81]
Desmodesmus sp. 750 42.25 – – [82]
Scenedesmus sp. 440 41.54 1.68 (H/C) – [83]
0.27 (O/C)

Macroalgae
Saccharina japonica 470 37.9 1.4 (H/C) – [84]
0.17 (O/C)
Porphyra tenera 500 47.4 – ∼37 [19]
Undaria pinnatifida 500 45.8 – ∼26 [19]
Saccharina japonica 450 47 – 33 [85]
Laminaria digitate 500 17 – ∼30 [86]
Fucus serratus 500 11 – ∼31 [86]

ash content, and (iv) less energy consumption ratio [17–19]. The
schematic illustration of typical pyrolysis processing of algae and the
pyrolysis end products is given in Fig. 1. The liquid product of pyrolysis
contains phenolic ethers, alkyl phenolics, heterocyclic ethers, polyaro-
matic hydrocarbons while, the solid char comprises of carbon, hy-
drogen, oxygen and gaseous products comprising of CO2, CO, CH4 and
H2 [20].
2.1. Effect of pyrolysis temperature on the product yield from algae
Temperature is the fundamental and crucial factor in pyrolysis
which ranges from 200 to 1000 °C for complete degradation of biomass
[13,21] and various research works have been undertaken to assess the
influence on pyrolysis temperature on bio-oil or solid char yield and
quality (Table 1). In consideration with the thermal decomposition of
algae, different ranges of temperature favour the stepwise decomposi-
tion reactions. For example, temperature below 200 °C is enough for
dehydration, which is followed by devolatilization (i.e., the actual
process of pyrolysis) in the temperature range of 200–550 °C and solid
decomposition at above 550 °C. In the dehydration process, water
bound moieties are removed from algae and in the devolatilization
process, volatile compounds are removed and biomolecules are de-
composed. Carbohydrates and proteins are decomposed at temperature
below 400 °C and lipids decompose at 550 °C. At temperature above
550 °C, solid decomposition occurs which involve: (i) secondary
cracking of larger molecular weight hydrocarbons into smaller mole-
cular weight components which leads to a decrease in the bio-oil con-
tent and (ii) recombination reaction occurs when the residence time of
volatile compounds in the reactor is too long [22–24]. Pyrolysis process
is classified into different categories: (i) slow pyrolysis, (ii) fast pyr-
olysis, (iii) flash pyrolysis, and (iv) catalytic pyrolysis depending on the
operating conditions such as temperature, heating rate, vapor and solid
residence times, catalyst types, etc. [13].
In slow pyrolysis, the temperature is gradually increased at a slow
rate for the degradation of biomass, typically ranging from 5 to 7 °C/
min characterized by long vapor residence times, usually for 10–30 s
[13,25] and the particle size for degradation ranging between 5 and
50 mm [26]. However, this process is quite useful for biochar produc-
tion since the other end products namely liquid and gaseous products
are produced at low quantities compared to solid products (char) [13].
Few studies have been reported for slow pyrolysis of microalgal bio-
mass for bio-oil production. For instance, bio-oil yield from Spirulina sp.
was 45% when the temperature is maintained at 550 °C for 60 min with
a heating rate of 8 °C/min. The energy consumption ratio was observed
to be 0.49 which is less than unity indicating a positive net energy
output [17]. Similarly, bio-oil yield from Spirulina platensis was 28.5%
when the temperature is maintained at 500 °C with a heating rate of
7 °C/min for the total reaction time of 60 min. Energy consumption
ratio for the above mentioned operating conditions was found to be
1.56 which is slightly higher than unity, indicating the reaction as net
energy consumer [27].
In fast pyrolysis, temperature is increased at a faster rate in the
absence of oxygen leading to fast heating of biomass for thermal de-
gradation. Rapid heating rate at 300–600 °C/min, a short vapor re-
sidence time and the particle size less than 1 mm [26,28] are generally
adopted for obtaining high grade bio-oil. Many microalgal species have
been reported to yield bio-oil in the range of 17 to 72 wt% from fast
pyrolysis process. Microalgal species such as Chlorella vulgaris, Ar-
throspira platensis, Nannochloropsis oculata, and Schizochytrium lima-
cinum have been examined under fast pyrolysis in the range of
400–700 °C with a heating rate of 80 °C/min [29]. However when
considering the bio-oil yield, 18% and 24% were obtained for Chlorella
protothecoides and Microcystis aeruginosa from fast pyrolysis with the
operating parameters of 500 °C, 600 °C/s heating rate and vapor

3
K. Brindhadevi, et al. Fuel 285 (2021) 119106

Fig. 2. Influence of reaction temperature of pyrolysis and HTL on bio-oil and biochar yield and quality.

residence time of 2–3 s [30]. Harman-ware et al. (2013) reported the amount of oxygen content [18]. Another catalytic pyrolysis was per-
bio-oil yield of 55% from fast pyrolysis of Scenedesmus sp. at 500 °C with formed using MgCe/Al2O3 based catalyst on Pavlova sp. which yielded
vapor residence time of 2 s. In another study, Chlorella vulgaris was 23% bio-oil, subsequently reducing the oxygen concentration from
reported to yield 53% bio-oil at a pyrolysis temperature of 500 °C [31]. 14.1% to 9.8% [43].
The biomass composition also poses significant effect on the bio-oil
yield which is substantiated by Belotti et al. (2014), where the nitrogen
3. HTl
starved C. vulgaris yielded 72% bio-oil at 400 °C with an energy con-
sumption ratio of 0.53 and high heating value. Also, it is noteworthy to
HTL is performed at subcritical temperature of water where water
mention that, nitrogen upon combustion releases NOX as atmospheric
acts as a lucrative and environmental friendly reaction medium for the
pollutants and its presence in bio-oil as heteroatomic (N) compounds
conversion of biomass into fuels. HTL, in general, performed in the
succumbs the refinery process from direct upgradation [32,33].
temperature and pressure between 280–370 °C and 10–25 MPa, re-
In the flash and catalytic pyrolysis, as the name suggests, biomass is
spectively, produces bio-oil and also solid residue (s), gases, and aqu-
heated within a fraction of seconds and the process is operated at
eous phase products [8]. The typical HTL processing of algal biomass
around 20 Mpa in a hydrogen rich atmosphere, with less residence time
into various products is illustrated in Fig. 1. The key aspect of HTL is the
in the reactor [13], heating rate greater than 1000 °C/s, which very
ability to use wet biomass without subjecting it to the drying process.
rapid than fast pyrolysis and the particle size less than 0.2 mm [26].
Water as the reaction medium under the above conditions has two
Flash pyrolysis is generally employed for yielding higher bio-oil content
major advantages in HTL: (i) it initiates the interaction with biomass
from biomass with a residence time of less than 1 s [34]. Bio-oil yield
and aid in breakage of chemical bonds between them, and ii) the ease of
also depends on the type of reactor vessel. For example, flash pyrolysis
separation of bio-oil from other components [44,45]. HTL entails a
of Chlorella vulgaris in an entrained flow reactor yielded 60.22 wt% of
series of structural and chemical transformation processes in the water
bio-oil at the pyrolysis temperature of 800 °C [35]. However, flash
medium, and broadly, it involves three steps; depolymerization, de-
pyrolysis of algal biomass in fluidized bed reactor by CFD modelling is
composition and recombination [8,12,46]. Bio-crude or bio-oil is highly
expected to yield 0.27 for bio-oil and 0.53 for non-condensable gases
dense: 0.97–1.04 kg L−1, highly viscous: 3.27–330 mPas, and a dark
[36]. Similarly, flash pyrolysis of macroalgae in pyrolysis centrifugal
liquid fuel obtained from various biomasses [24]. Biocrude comprises of
reactor yielded 78% energy recovery in bio-oil with a residence time of
mainly phenolics, aromatic hydrocarbons, nitrogen containing com-
0.8 s, at a reaction temperature of 550 °C and a feeding rate of
pounds, amides, fatty acids and esters [47]. With reference to the
340–990 g/hr [37]. Moreover, the stability and quality of bio-oil is a
gaseous products obtained from HTL, hydrogen, carbon dioxide, carbon
major concern. Concerning the composition of bio-oil, the presence of
monoxide, and methane are present in the gaseous products in the
high oxygen content in bio-oil creates problematic issues during the
percentage of 23.7%, 19.1%, 22.8%, and 25.8%, respectively [48].
production process wherein its direct use in refineries for transportation
Regarding the experimental reactors or systems for HTL, it is carried out
is not recommended. Therefore to enhance the bio-oil quality with less
mostly in batch autoclaves (10–100 mL), large batch reactors, and
oxygenic compounds, several catalysts have been used for the pyrolysis
continuous reactors [47].
of biomass [13]. Catalysts such as Ni supported Zeolite [38], Na2CO3
[39], H+ZSM-5 [40,41] have been widely reported in the pyrolysis of
algal biomass. A research was carried out using Ni-Ce/Al2O3 catalyst for 3.1. Mechanism of temperature impact in HTL
the pyrolysis of Nannochloropsis sp. where the bio-oil yield was 23.28%
when operated at 500 °C [42]. Indeed, the follow up study of Ni-Ce/ Among the different reaction parameters, the physical and chemical
Al2O3 catalyst on other microalgal species were performed where the features of bio-oil rely on biochemical composition of algae and reac-
catalytic pyrolysis of Tetraselmis sp. yielded 25.86% bio-oil using Ni-Ce/ tion temperature [47]. In HTL of biomass, the reaction temperature
Al2O3 and 25.83% using Ni-Ce/ZrO2 catalyst; whereas, for Isochrysis sp., affects the production of bio-crude and its composition as the ionic
25.49% of bio-oil was obtained when using Ni-Ce/ZrO2 catalyst. These characteristics of water changes with respect to reactor temperature
ceria based catalysts removed 15–20% N content and also significant that accelerates various reactions [49]. The impact of temperature on
the bio-oil yield and composition is illustrated in Fig. 2. The two

4
K. Brindhadevi, et al. Fuel 285 (2021) 119106

competitive reactions such as hydrolysis and repolymerization dom- Table 2

inate one another based on the temperature regime, i.e., hydrolysis Effect of HTL temperature on the quality and quantity of bio-oil.
dominates repolymerization at low reaction temperature whereas re- Strains Temperature (°C) Bio-oil Atomic ratios References
polymerization takeover or competes for hydrolysis at high temperature (%) of bio-oil
[50–52]. Decarboxylation of amino acids yields amino compounds and
Chlorella vulgaris 300 29.37 – [48]
carbon dioxide by removing oxygen from the biomass and at the same
Scenedesmus 400 60.9 1.516 (H/C) [58]
time, deamination of some amino acids produce carboxylic acids and almeriensis 0.021 (O/C)
ammonia by removing the nitrogen from biomass. On the other hand, Nannochloropsis 400 51.7 1.622 (H/C) [58]
decarboxylation of fatty acids produces alkanes and alkenes, and the gaditana 0.025 (O/C)
degradation of reducing sugars produce cyclic oxygenates in the same Chlorella 350 94.8 – [87]
Nannochloropsis sp. 350 43 1.63 (H/C) [88]
100 to 200 °C temperature regime [51]. However, according to another
0.089 (O/C)
report [53], lipids are composed of three fatty acids held by a glycerol 0.044 (N/C)
backbone. When the temperature is increased to values > 300 °C, lipids Nannochloropsis 290 54 0.13 (H/C) [89]
are broken into fatty acids and hydrophilic glycerol and then, the oceanica 0.08 (N/C)
0.15 (O/C)
produced fatty acids could be decomposed into hydrocarbons (alkanes).
Galdieria sulphuraria 350 27.5 – [90]
As described by Kumar & Gupta [54], at ambient temperature, Phaeodactylum 350 39 – [91]
water is a polar solvent with a boundless network of H-bonds and it tricornutum
does not solubilize organic compounds. When the temperature is in- Tetraselmis sp. 350 65 1.6 (H/C) [91]
creased to the vicinity of the subcritical zone, the H-bonds of the water Nannochloropsis sp. 600 66 – [92]
Cyanobacteria sp. 325 21.10 – [93]
start weakening; the ionization constant (kW) of water begins to in-
Bacillariophyta sp. 325 18.21 – [93]
crease at about 3 orders of magnitude higher than the water at ambient Arthrospira platensis 350 35 – [94]
temperature. Hence, acidic hydronium ions (H3O+) and basic hydro- Tetraselmis sp. 350 40 – [94]
xide ions (OH−) are uusally dissociated, which makes subcritical water Nannochloropsis sp. 260 55 – [95]
an acidic medium for hydrolyzing biomass. On the other hand, low Chlorella sp. 220 82.9 – [95]
Arthrospira platensis 310 45 – [96]
dielectric constant allows the solubility of certain salts considerably, i.e. Chlorella sp. 350 27.3 – [64]
the dissolution of NaCl is higher in subcritical water followed by Nannochloropsis sp. 250 20.2 1.68 (H/C) [97]
Na2SO4 [12,55]. The amide compounds are produced from the long 0.11 (O/C)
chain fatty acids by replacing their hydroxyl groups by ammonia (from 0.061 (N/C)
Nannochloropsis sp. 350 48.67 – [98]
deamination of amino acids), and esters are produced from the reaction
Pavlova sp. 350 47.05 – [98]
between the fatty acids with the alcohols (from the reduction of an Dunaliella tertiolecta 360 25.8 – [99]
organic acid). Besides, N&O-heterocyclic compounds such as pyrrole, Spirulina sp. 260 43.05 – [10]
pyridine, pyrrolidinone, pyrrolidinedione, imidazole, thiazole, and Nannochloropsis salina 350 46 – [100]
their derivatives are formed from the Maillard reaction between amino Nannochloropsis sp. 300 48.23 – [57]
Enteromorpha prolifera 290 28.4 – [101]
acids, and reducing sugars and further, certain nitrogen and oxygen Chlorella pyrenoidosa 280 50 – [102]
heterocyclic compounds might react with long chain fatty acids to form Chlorella pyrenoidosa 280 57.3 – [103]
pyrrolidinone derivatives of fatty acids [51,56].
Macroalgae
Oedogonium sp. 350 26.2 – [59]
3.1.1. Effect of temperature on the yield and composition of bio-oil in HTL Derbesia tenuissima 350 19.7 – [59]
There are several research works that have discussed the impact of Enteromorpha prolifera 300 23.0 1.43 (H/C) [104]
Mixed culture algal 300 50 0.050 (N/C) [105]
reaction temperature on the yield and composition of bio-oil (Table 2).
biomass 0.30 (O/C)
HTL reaction temperature of 300 °C was found to yield higher bio-crude
from Nannochloropsis, at about 48.23% with 89.28% HTL conversion
efficiency in the presence of Ni/TiO2 catalyst [57]. In another recent macroalgae, Oedogonium yielded greater bio-oil at about 26.2%,
investigation, 300 °C was identified to be optimal and produced 29.37% whereas Derbesia yielded higher bio-oil of 19.7% amongst marine
bio-oil from Chlorella vulgaris with other conditions such as 60 min, 3% macroalgae. However, the elemental composition of bio-crudes ob-
nano ZnO catalyst and 15 g/200 mL biomass loading [48]. tained from both fresh and marine macroalgae showed similar pattern
During CO2- HTL, the CO2 addition elicits the hydrolysis rate of with 33–34 MJ kg−1 HHV. This study also reported bio-crude pro-
biomolecules owing to the formation of carbonic acid, which acts as an ductivity for Derbesia, Ulva and Oedogonium as 2.4, 2.1, and
acid catalyst [12]. Further, rapid heating of reactor is preferable to 1.0 g m−2 d−1 respectively [59].
avert the depolymerization reaction and the degradation of certain With reference to the effect of temperature on the elemental com-
biopolymers prior to the reach suitable temperature. For example, the position of bio-oil, reaction temperature between 270 and 330 °C
hydrolysis of cellulose is tenfold higher in the vicinity of 240 and yielded bio-oil with 4.7% nitrogen and it is lowered to 4% when the
310 °C, and specifically at 280 °C, 2 min residence time, 100% cellulose temperature was increased to 370 °C [60]. Similarly, extending the re-
conversion was observed. However, better decomposition of glucose action temperature of HTL of Spirulina Platensis from 250 °C to 350 °C
was observed at 250 and 270 °C [12]. In Scenedesmus almeriensis, the reduces the nitrogen content in bio-oil from 3.8% to 1.61% and also
higher bio-oil content of 60.9% was observed at 400 °C HTL tempera- decreases the content of nitrogen containing compounds to 10% [61].
ture with H/C and O/C ratios of 1.516 and 0.021 respectively [58]. In a In general, GC–MS analysis of bio-oils produced from the HTL of algal
very recent study, the effect of temperature, time, and catalyst con- biomasses carried out under different temperature showed cyclic oxy-
centration of HTL process on the yield and composition of bio-oil from genates, N & O-heterocyclic compounds, straight & branched amides,
Spirulina was evaluated and a reaction temperature of 260 °C increased esters, ketones, hydrocarbons, alcohols, and fatty acid derivatives [51].
the bio-oil yield up to 43.05% in 30 min time and 5% catalyst with Similarly, composition of bio-oil obtained from Spirulina indicates the
27.28–36.01 MJ/kg higher heating value (HHV) [10]. In addition to the presence of amides, esters, nitriles, hydroperoxide and alkanes [10].
exploitation of microalgal species for bio-oil production, six outdoor From the literature, it is perceived that the content and profile of bio-
cultivated macroalgal species were converted into bio-oil in a batch crude depends on the temperature and increasing temperature was
reactor via HTL. The impact of biochemical composition of algae on the found to increase the bio-crude yield in microalgae [62–64]. Maximal
yield and composition of bio-oil was analysed. Among the freshwater

5
K. Brindhadevi, et al.
bio-oil content under high reaction temperature is owing to two key
phenomena, i.e., a high ionic product of water and low dielectric con-
stant. At high water temperature, the high ionic product of water
(Kw = [H+][OH−]) provides dissociated H+ and OH− ions, which
drives acid and base-catalyzed reactions [65,66], and during this pro-
cesses, biomass components undergo isomerization, reforming, depo-
lymerization and repolymerization to yield bio-oil [49]. In HTL tem-
perature region, the ionic product of water (Kw) is high at about 10−12
compared to 10−14 for ambient water [12]. This property of water
favours the formation of oil products by having ionic bond between
water and biomass, thereby reducing the formation of solid char or gas
by means of blocking the radical reactions [67]. At the same time, the
dielectric constant (ε) of water decreased from 80 to 20 in the sub-
critical temperature [54]. More specifically, the dielectric constant of
water drops down from 78 Fm−1 to 14.07 Fm−1 when the temperature
and pressure are raised from 25 °C and 0.1 MPa to 350 °C and 20 MPa,
respectively [12]. The low dielectric constant makes water a hydro-
phobic solvent, allowing to dissolve hydrophobic organic compounds
like free fatty acids [54,68,69]. On the other hand, conditions that
enhance the yield of liquefaction products are achieved at supercritical
conditions. Also, attaining supercritical condition is cost effective due
to its variability in specific heat capacity and low compressibility of
liquids [67,70]. With respect to product yield from HTL, temperature
greatly influences the formation of various products such as biochar,
bio-oil and syngas. For yielding high amount of bio-oil, intermediate
temperature of 300–350 °C is advantageous because of the following
facts: (i) at temperature higher than the activation energy of bond
dissociation, secondary decompositions and boudouard reaction (reac-
tion of solid char with CO2 to produce carbon monoxide) occurs which
leads to the formation of more gaseous products, (ii) at higher tem-
perature, there is an increased char formation because of condensation
of free radicals, (iii) at lower temperature, the decomposition of bio-
mass is incomplete which does not yield sufficient bio-oil, and (iv) at
higher temperature, operational cost is high and bio-oil yield is low
[71–73]. This implies the importance of temperature in HTL reactions
for yielding the desired liquefaction products.
4. Conclusions, opportunities and future research
Increased utilization of fuels from non-renewable and unsustainable
sources has led to explore renewable, non-toxic, alternative fuels. In
this quest, biofuels from various renewable sources such as plant oils,
animal fats, and algal lipids have gained interest in producing sus-
tainable (bio) fuels. Among the sources, microalgae is considered to be
a better and simple option as they harvest light energy and mitigate CO2
for generating biomass for bioenergy. Further, various thermochemical
methods are being pursued to convert dried or wet algal biomass into
bio-oil or biochar or other gaseous products. In this track, HTL (sub-
critical) and pyrolysis (supercritical) techniques are widely used for
transforming the complete algal biomass irrespective of the biochemical
composition into bio-oil or char products. Hence, the core subject of
this review was to discuss the works carried out on HTL and pyrolysis of
several algal species to produce crude oil to substitute petro-crude. The
mechanism and operation of HTL and pyrolysis processes were initially
described. Further, this article comprehensively presented the me-
chanisms involved and the effect of reaction temperature on the process
efficiency of HTL process. Further, the influence of reaction tempera-
ture in HTL and pyrolysis on the yield, quality and properties of bio-
crude were discussed in detail. HTL and pyrolysis can yield better en-
ergy rich fuels for the countries where extensive biomass resources are
available. In such case, bio-oils that are claimed to be carbon neutral or
greenhouse gas neutral with traceable or no zero SOX emissions can be
profoundly used. Though higher bio-oil content is produced from algae
through pyrolysis and HTL, it has high heteroatoms akin N, O, S rela-
tively to petro-crude, and thus, decreasing heteroatoms in bio-oil is a
present day challenge and it demands further research and
6
Fuel 285 (2021) 119106
development.
Declaration of Competing Interest
The authors declare that they have no known competing financial
interests or personal relationships that could have appeared to influ-
ence the work reported in this paper.
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