Fuel 283 (2021) 119190

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Fuel
journal homepage: www.elsevier.com/locate/fuel

Review article

A review on the pyrolysis of algal biomass for biochar and bio-oil –

Bottlenecks and scope
Manigandan Sekar a, Thangavel Mathimani b, Avinash Alagumalai c, Nguyen Thuy Lan Chi d,
Pham Anh Duc e, Shashi Kant Bhatia f, Kathirvel Brindhadevi g, *, Arivalagan Pugazhendhi d
a
Department of Aeronautical Engineering, Sathyabama Institute of Science and Technology, Chennai, India
b
Department of Energy and Environment, National Institute of Technology Tiruchirappalli, Tiruchirappalli - 620 015, Tamil Nadu, India
c
Department of Mechanical Engineering, GMRIT, Rajam 532127, Andhra Pradesh, India
d
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
e
Faculty of Environment and Labour Safety, Ton Duc Thang University, Ho Chi Minh City, Viet Nam
f
Department of Biological Engineering, College of Engineering, Konkuk University, Seoul 05029, Republic of Korea
g
Institute of Research and Development, Duy Tan University, Da Nang 550000, Viet Nam

A R T I C L E I N F O A B S T R A C T

Keywords: Algae become reasonable feedstock in recent times for biofuel production as they are environmentally benign,
Biochar sustainable and renewable biomass. Biofuels are produced from algal biomass by chemical, biochemical, and
Bio-oil thermochemical methods. Among the thermochemical techniques, pyrolysis is a well-known method involving
Thermochemical
high temperature and high pressure to produce biochar and bio-oil from numerous algal biomasses. Therefore,
Slow pyrolysis
Fast pyrolysis
this review was undertaken to collate and discuss different pyrolytic processes employed for the conversion of
Catalytic pyrolysis algal biomass into biochar and bio-oil production. At the outset, different pyrolysis methods slow pyrolysis, fast/
flash pyrolysis, catalytic pyrolysis, microwave assisted pyrolysis and hydropyrolysis operated for the conversion
of various microalgae and cyanobacteria into biochar and bio-oil were reviewed using copious literature.
Further, challenges arisen out of using above-said pyrolysis methods were critically highlighted to pave the way
to choose an appropriate pyrolysis method for obtaining desirable quantity and quality of bio-oil from algae.

1. Introduction associated with the utilization of algae as third generation feedstock

Concerns over fossil fuels availability and emission index increases
research and development on renewable fuels and thus, biofuel has
gained profound attention in recent times owing to its renewable and
environmental friendly aspects [1,2]. Biofuel from biomass is a prom­
ising source of renewable energy. Biomass evolution for biofuel typically
classified into three generation. First and second generation fuels
depend on the edible crops and non-food biomass. Although they impart
various benefits, they have certain limitations of plantations [3], higher
NOx emission [4] and surplus land requirement. In recent decades, the
number of works investigating microalgae as biofuel feedstock had
widely increased compared to lignocellulosic biomass owing to their
various advantages. Algae gained lime light due to following reasons
such as high growth rate, high yield, CO2 capture, and non-feed stock
[5,6]. Besides above-said merits, there are many other benefits
[7,8], which includes higher lipid productivity, rapid growth, less land
requirement. Although there are series of studies conducted on the
conversion of microalgae into useful energy still it was challenging due
to the cultivation and post processing of algae. Microalgae can be used
for biodiesel, jet fuels and Fischer-Tropsch fuels production as well. In
addition to biodiesel production, algal biomass can also be converted
into bio-oil and biochar through three main thermochemical routes such
as gasification, liquefaction and pyrolysis [9]. Among them, pyrolysis
has acquired prominent attention due to its operating conditions and
yield [10].
Pyrolysis is a simple thermochemical process which operates in the
oxygen free atmosphere from the temperature range from 300 to 700 ◦ C.
The main products of the pyrolysis are bio-oil, bio-char and gaseous
component [11]. Liberation of the main product depends on the tem­
perature, residence time and type of feedstock. By varying above two,

* Corresponding author.
E-mail addresses: kathirvelbrindhadevi@duytan.edu.vn (K. Brindhadevi), arivalagan.pugazhendhi@tdtu.edu.vn (A. Pugazhendhi).

https://doi.org/10.1016/j.fuel.2020.119190
Received 27 May 2020; Received in revised form 13 August 2020; Accepted 5 September 2020
Available online 30 September 2020
0016-2361/© 2020 Elsevier Ltd. All rights reserved.
M. Sekar et al.
the main product can be varied based on the requirement. Bio-oil and
bio-char can be used as the essential source to generate heat by com­
bustion process. Meanwhile, bio-char used as the activated carbon,
fertilizers, soil compost and efficient catalyst for biofuel production.
There are different pyrolysis based on the conditions such as slow, fast,
flash, microwave assisted, and hydrolytic pyrolysis. Each pyrolytic
process has its own merits and demerits. Composition and yield of bio­
char depends on the temperature and other conditions used in pyrolysis.
Hence, it is imperative to understand the processing conditions of py­
rolysis to ascertain the pertinent pyrolytic process for obtained desirable
quality and yield of biochar. The key products bio-oil, bio-char and gas
depends on the temperature, residence time, pressure, biomass nature,
and other reactor conditions. Furthermore, the concentration of solid,
liquid and gas can be altered by choosing the optimized pyrolysis pro­
cess and the microalgae species. Therefore, this review was undertaken
to review the different pyrolysis techniques. This study gives the recent
trends in conversion of microalgae into useful bio-oil and bio-char
through slow, fast, flash, microwave assisted, catalytic, and hydrolytic
pyrolysis. The underlying mechanism of pyrolysis of biomass compo­
nents such as carbohydrates, protein, lipids were comprehensively
addressed using published literatures to comprehend the complete py­
rolysis process. Eventually, conclusion and scope of the pyrolysis process
was signposted to pave the way for foreseen research endeavours.
2. Pyrolysis of microalgae
Among the various thermochemical processes, pyrolysis has received
considerable attention in recently due to its simplicity and speed and
further, pyrolysis technique can yield versatile products (liquid), which
are quite easy to handle unlike other thermochemical biomass conver­
sion techniques [12–14]. Main products of the microalgae pyrolysis are
biochar, bio-oil and non-condensable gases. Pyrolysis is classified into
many types based on the difference in operating conditions namely,
slow, fast, flash, microwave assisted, catalytic, and hydrolytic pyrolysis
(Fig. 1).
2.1. Slow pyrolysis
In general, slow, fast and flash pyrolysis depends on the heating rate,
and vapor residence time and sometimes temperature. In slow pyrolysis,
temperature is increased slowly with slow heating rate. Vapors persist in
the slow pyrolysis reactor between 10 and 60 min are majorly used for
biochar production. The hearting rate in the slow pyrolysis reactor is in
the range 0.1 and 1℃/s and bio-char, bio-oil or gas can be produced as
the main product based on the process conditions [15]. During the
Fig. 1. Different pyrolysis techniques for the conversion of microalgal biomass
into solid, liquid, gaseous products.
2
Fuel 283 (2021) 119190
process, the microalgae placed in the reactor and heated using the
electric furnace at the rate of <10 ◦ C s− 1. The slow pyrolysis process
carried out in absence of oxygen. Nitrogen gas used as the sweeping gas
to avoid oxygen presence inside the reactor. Slow pyrolysis is greatly
beneficial for biochar yield as other liquid and gaseous products are
obtained in minimal level relatively to biochar [16]. During slow py­
rolysis, the biomass is decomposed at the temperature intervals of
400 ◦ C to 500 ◦ C at different stages. Initially, bond breaking and water
content is removed. In second stage, lipids, proteins and carbohydrates
are decomposed due to the formation of pyrolysis. At the final stage,
carbon rich residues are formed. When the temperature range was be­
tween 450 and 550 ◦ C, the yield of organic liquid was between 50 and
70% w/w [17]. In a study, production of bio oil is high at the optimum
temperature of 500 ◦ C [18] and similar results were obtained by Bordoli
et al. using Scenedesmus dimorph [19]. Grierson et al. investigated the
slow pyrolysis using six microalgae species [20]. The observed oil and
bio char yields were 24–43% w/w and 34 to 63% w/w. The role of
temperature and catalyst in the slow pyrolysis also plays a crucial role.
Addition of catalyst increases the heating value of the liquid. Mean­
while, the yield rate increased by 48% by the influence of Nanno­
chloropsis sp. catalyst. Despite higher yield, the use of Nannochloropsis sp.
catalyst is limited owing to the production of charcoal as main product
[21]. On the other hand, use of Chlorella sp. increases the yield of py­
rolysis oil, high heating value, reduced pH and lower density owing to
the less oxygen content than lignocellulosic [22]. Microalgae can be
pyrolyzed in both slow and fast process. Based on the temperature and
the heating rate their methods are classified as slow and fast/flash.
Depends on the nature of the microalgae the method had been chosen.
For instance, in some cases it is quite necessary to observe the degra­
dation of the materials at slower rate in that scenario the slow pyrolysis
is opted. Usually slow process is used for char production. Significance is
vapor remains in the reactor up to 60 min with low heating rate of 0.1
and 1 ◦ C s− 1. Slow pyrolysis wide used due to its easy operation nature.
However, slow heating leads to high yield of solid residues and gaseous
products. Li et al. further classified the process into two sub divisions
based on main product and working temperature as carbonization and
conventional [23] based on the main product. In carbonization the main
product is char and the optimum working temperature is 400 ◦ C. In the
other end, the conventional process is used to produce the gaseous,
liquid and char products at the temperature of 600 ◦ C [24]. From the
above understanding, temperature governs the crucial role on slow py­
rolysis. It is evident that increasing the temperature enhances the bio-oil
production up to the optimum temperature of 500 ◦ C, as the tempera­
ture elevated above 500 ◦ C, the production yield is decreased. For
instance, the yield of char from the slow pyrolysis is 66% at 300 ◦ C and
the average production rate is 40% with the calorific value of 36 MJ/kg
[25]. Grierson et al. performed notable work on thermal characteristics
of the microalgae under slow pyrolysis. The study was conducted on
aquatic microalgae Tetraselmis chui, Chlorella like, Chlorella vulgaris,
Chaetoceros muelleri, Dunaliella tertiolecta and Synechococcus. The sam­
ples are collected and analyzed with computer aided thermal analysis
[20]. The rate of biogas compounds vary from 1.2 to 4.8 MJ/kg. Besides,
the energy requirement for the biomass at 500 ◦ C was 4.8 MJ/kg. Akhtar
et al. analysed the waste water derived algae and lignocellulosic be­
tween 400 and 600 ◦ C to produce the biochar from the biomass. A waste
water grown alga produces the high yield than the palm branches.
However the ash content is higher and less stable. In regard to the energy
yield and cost, microalgae are most economical and significant [26].
Moreover the biochar produced from the palm and algae can be
employed for energy application and wastewater treatment respectively.
In earlier studies, the Chlorella protothecoides used widely owing to its
higher lipid content with the maximum yield of liquid (52–55% w/w),
gas (33–36% w/w), and bio-char (15% w/w) [27,28]. The yield had
been improved by increasing the temperature from 300 ◦ C to 500 ◦ C. For
instance, raising the 200 ◦ C increases the gaseous products from 9.5% to
40.6% w/w. In other end, the concentration of hydrogen concentration
M. Sekar et al. Fuel 283 (2021) 119190

increased by 52% vol. Since the microalgae gained the lime light, the
pioneers started to focus on Chlorella sp. based on the temperature the
microalgae produces maximum liquid yields. For instance, Chlorella sp.
reports 40%w/w (425 ◦ C), Chlorella vulgaris record 60.7% w/w (500 ◦ C),
Dunaliella salina produces 64.9% w/w (500 ◦ C) and Spirulina sp. report
46% w/w (550 ◦ C) [3,17,18,29]. From the above it is obvious as the
temperature raises the yield increases up to 500 ◦ C. Provided that,
pretreated the microalgae with Na2CO3 reduces the decomposition
temperature and low bio-oil yield than conventional biomass.
Bordoloi et al. demonstrated the pyrolysis of Scenedesmus dimorphus
obtained the highest yield 39.6% wt of bio-oil at the temperature ranges
form 300–600 ◦ C [19]. The 10.6% and 6 wt% of nitrogen present in the
bio-oil and bio-chars. Further, the species such as amides, indoles and
nitriles were also found in the yield. This denotes large proportion of the
nitrogen retained during the process [30,31]. In addition to temperature
and operating conditions, the limitations of cracking, time and extra
energy made this process not popular in recent days [30].

2.2. Fast/ flash pyrolysis

Fast/flash pyrolysis operates at high heating rate with less residence

time [16], specifically the heating rate was 1000 ◦ C s− 1 with > 0.2 mm
biomass particle size [32]. Fast pyrolysis involves very higher heating
rate, shorter residence time, high heat transfer rate and speedy cooling
of pyrolysis vapor [33]. In the fast pyrolysis process, the higher pyrolysis
temperature is reached before decomposition of the product. Fast py­
rolysis is a rapid heating process widely used for high bio-oil production
and the content of sulphur and nitrogen is low, which makes easy Fig. 2. Typical pyrolysis reactor of algal biomass for biochar and bio-
handling. oil production.
The biochar or bio-oil yield from fast or flash pyrolysis varies
depending upon feedstock (Table 1). The peak temperature of the pro­ gas.
cess varies case to case. In some conditions, the peak temperature is Fast pyrolysis is a preferred technique for production of pyrolysis oil
below 500 ◦ C and in some other conditions the temperature is high as from biomass due to low secondary cracking, poor condensation and
900 ◦ C. Besides the heating rate is very high as 600 ◦ C s− 1 [34,35]. Miao least polymerization. There are several species however
and Wu investigated the influence of Chlorella protothecoides bio-oil yield C. protothecoides, M. aeruginosa, and Scenedesmus sp. are widely used in
by using fast pyrolysis. They observed the production of bio-oil from fast pyrolysis process owing to its maximum liquid yields. The liquid
heterotrophic is 3.4 times higher than the autotropic cells. Further, using yield of C. protothecoides, M. aeruginosa, and Scenedesmus were 17.5% w/
of Chlorella protothecoides and Microcystis aeruginosa, increases the oil w at 500 ◦ C, 23.7%w/w at 500 ◦ C and 51.8% w/w at 440 ◦ C [33,37].
yield by 29–33%. [31,36]. A typical pyrolysis reactor is illustrated in The yield for C. protothecoides is low due to poor heat transfer in the
Fig. 2. However, fluidized beds are generally used for the fast pyrolysis reactor. Campanella and Harold determined the effect of carrier gas and
process. The biomass feed into the electrically powered reactor. The the catalyst on the pyrolysis of green algae. H, Fe, Cu and Ni catalyst are
main components of the fast pyrolysis are feeders, condenser and carrier dispersed with green blue microalgae [38]. Addition of catalyst in­
creases the bio-oil/ liquid yields at the ratio of 0.7 and 0.78. Based on the
Table 1
nature of the catalyst, the yield of main product varies. For instance,
Slow, fast, microwave assisted and catalytic pyrolysis of several microalgae for Nickel and molybdenum based catalyst reports higher amount of hy­
biochar/bio-oil production. drocarbons and aliphatic alkenes due to the decarboxylation of
oxygenated chemicals [38–40]. The other typical catalysts are CeO2,
Feedstock Pyrolysis type Bio-oil Biochar Reference
yield yield TiO2, Al2O3 and hydrotalcite. Chen et al. studied the Nannochloropsis sp.
along with bamboo waste [41]. They observed to increase in the bio-oil
Chlorella vulgaris Slow 41 – [20]
Spirulina platensis Slow 23–29 28–40 [82]
production as the blend ratio of the bamboo waste increases. The main
Chaetocerous Slow 33 – [20] significance of the bamboo waste is suppression of nitrogen into gas
muelleri phase. Maliutina et al. observed the effect of pressure on C. vulgaris
Chlorella vulgaris Catalytic (MgO) 20 16 [59] during pyrolysis [42]. Increasing the pressure reduces the volatile
Chlorella vulgaris Catalytic (ZnCl2) 37 17 [59]
release which leads to higher bio-char formation as the pressure main­
Nannochloropsis Catalytic (HZSM-5) 21–31 26–46 [21]
Chlorella Catalytic (biochar 47 16 [83] tained above 1 MPa. Elevated pressure increases the bio-oil from 27.16
sorokiniana based catalyst) area% (0.1 MPa) to 46.60 area% (1.0 MPa). In this process the particles
C. protothecoides Fast 58–72 – [31] are resized less than 1 mM before transferring to the reactor. The flue gas
Dunaliella Fast 39–43 22–36 [84] from the reactors is collected for drying the raw materials.
tertiolecta
Isochrysis Non- catalytic ~25 ~31% [60]
Fast pyrolysis technology is very advantageous if the main product is
Isochrysis Mg-Ce/Al2O3 ~21 ~33 [60] bio-oil. Although the production of main product depends on the feed
Isochrysis Ni-Ce/ZrO2 ~25.83 ~26 [60] stock, typically fast pyrolysis produces 60–75% of bio-oil, 15–25% of
Tetraselmis Non-catalytic 24.3% 22% [60] biochar and 10–20% of gaseous [43]. The production of main product
Tetraselmis Ni-Ce/Al2O3 25.86% ~19% [60]
typically higher than slow pyrolysis due to the high heating rate and
Tetraselmis Ni-Ce/ZrO2 25.83% ~17% [60]
Nannochloropsis Microwave 28.6 – [85] operating condition. Moreover, cultivate type also plays a role on the
Chlorella sp. Microwave 41–57 26–49 [86] bio-oil yield. Miao and Wu, Zainan et al. [31,35] demonstrated a study

3
M. Sekar et al. Fuel 283 (2021) 119190

on effect of cultivation process on bio-oil yield. The study was carried
out in two different cultivation stages such as heterotrophic and auto­
trophic using Chlorella protothecoides algae. Cultivation of microalgae
Chlorella protothecoides generates 3.4 times of higher bio-oil by fast py­
rolysis at heterotrophic than autotrophic. It is a special type of fast py­
rolysis. Flash generally means higher reaction temperature, rapid
heating and less vapor residence time. Further, the particles used in the
flash pyrolysis are very fine compared to slow and fast pyrolysis [44,45].
The main advantage of this process is high biomass to liquid conversion
rate. It is reported that fast pyrolysis of Fucusvesiculosus, Chorda filum,
Laminaria digitata, F. serratus, L. hyperborea, and Macrocystis pyrifera,
yielded numerous favorable compounds with low molecular weight
oxygen and nitrogen containing compounds at slower heating rates
[46]. On the contrary, the effectiveness of the yield were affected due to
acidic, unstable, viscous, and solubility nature of the biomass. Thus,
introduction of catalytic cracking and hydrogenation is obligatory.
2.3. Catalytic pyrolysis
In general, bio-oil obtained from the slow and fast pyrolysis process
consists of oxygen content. To improve oil stability by averting poly­
merization, condensation reactions, oxygen content of the bio-oil need
to be reduced [15]. In order to reduce the oxygen content in the bio-oils,
the catalysts are added. As shown in Table 2, elemental composition of
bio-oil and biochar obtained from different pyrolysis techniques is dif­
fers and addition of catalyst improves the pyrolysis process by reducing
the oxygen and nitrogen content in the bio-oil. Further, the catalyst
modifies the reaction process for generating upgraded bio-oil [30].
Furthermore, the operating temperature lies between 300 ◦ C to 600 ◦ C.
Tubular fixed bed reactors are used for the catalyst pyrolysis process.
Similar to fast process, this also contains the electrical powered reactor
which contains biomass and quarts wool. Further the inert gases are
used for condensation process. The catalyst process further classified
into two subgroups such as catalyst bed (biomass and catalyst are
inserted in stages) and catalyst mixing method (biomass and catalyst
premixed before entering the reactor) [47]. The bio-oil obtained from
the conventional process is poor in quality due to the high viscosity,
water content and acidity. Application of catalyst into the pyrolysis
improves the quality of main product by cracking the biomass into lower
molecular weight. The biomass treated with catalyst produces rich bio-
oil which is more stable and less acidic. The catalysts are classified into
two types acid and base. From the notable work it is evident that, acidic
catalyst produces high bio-char and base catalyst produces higher bio-oil
[48,49]. All catalyst used for producing the liquid and solid product
contains higher aromatic hydrocarbons. As of now, limited number of
catalysts was used in pyrolytic process to obtain desirable bio-oil.
Among the catalysts, nickel based catalysts revealed better perfor­
mance in pyrolysis as it will activate decarboxylation and decarbon­
ylation reactions during hydrodeoxygenation process [50]. In this
regard, other metal catalysts like Ce, Ti, Co, Mg, and Al were not re­
ported to be efficient catalysts on the distribution of pyrolysis products
(nitrogenated products) [51]. Despite the several catalysts, Zeolite based
catalyst are widely used in several notable studies owing to lower acid
content, high heating value, pore structure and enhanced aromatics
[52]. Zeolite contains higher aromatic hydrocarbons, and lower
oxygenated compounds due to the Bronsted-Lewis acid [53]. To improve
the effectiveness of the catalyst, the Zeolite modified with metal ions to
generate higher yield of bio-mass and hydrocarbon formation. Some
remake catalysts are Pt, Ni, Ce, Ni, Ce, Mg, Ce and Co, Mo [54–58].
Further, increasing the ratio of catalyst from 0% to 10% decreases the
residue yield of C. vulgaris. For instance, the production of solid residue
decreases from 19% to 10% due to the faster pyrolysis rate and activated
energy [59].
Ceria based catalysts were employed for the catalytic pyrolysis of
Tetraselmis sp. and Isochrysis sp. to investigate the quality and yield of
pyrolysis products in fixed bed reactor [60]. Alumina based catalyst was
found to be not ideal for Isochrysis alga as it showed reduced bio-oil and
syngas yield whereas CeO2 and zirconia supported catalysts had positive
effect. It may be due to the catalyst acidity and dehydration with the
production of charred species. Further, Ni-Ce/ZrO2 catalyst showed
25.49% bio-oil yield for Isochrysis. For Tetraselmis, Ni-Ce/Al2O3 and Ni-
Ce/ZrO2 has positive effect on bio-oils yield as 25.86 and 25.83%
respectively compared to bio-oil yield (24.34%) obtained from non-
catalytic pyrolysis. Interestingly, HHV of bio-oil were 34–35 MJ/kg
with low levels of oxygen i.e. reduced from 40 to 41% to 9–15% and
15–20% of N content was reduced in bio-oil obtained via ceria based
catalysts. It is further confirmed by 1H NMR and GC–MS analysis that,
higher aliphatic compounds and lower nitrogen compounds were pre­
sent in bio-oils. It is due to the cracking activity of Ni and combined
impact of Ce-Al and Ce-Zr, in which, CeO2 augments stability, dispersion
of Ni and carbon suppression [61].
Yu et al. observed the catalytic characteristics of the fast pyrolysis of
microalgae and the results validated over oil shale. Gas chromatography
mass spectrometer is used to find the characteristics of fast pyrolysis. It
had been observed, 600 ◦ C is the optimized temperature for higher yield
of aromatics, alcohol and phenol. From the vital study it’s been found
pyrolysis temperature is an most critical factor to bong cleavage [62].
Gautam and Vinu, found the non-catalytic fast process produces high
aromatic and aliphatic hydrocarbons [63]. To understand the effect of
catalyst, the test was performed with presence of Co-Mo/Al2O3 at the
optimized temperature of 500 ◦ C using Nannochloropsis oculata. Usage of
catalyst increases the formation of olefins and fatty nitriles [63].
2.4. Microwave assisted pyrolysis (MAP)
MAP uses microwave irradiation for pyrolysing microalgae biomass
to produce bio-oil and biochar products. Microwaves are in the form of
electromagnetic radiations in the radio frequency range from 0.3 to 300
GHz. The wavelength ranges from 1000 to 1 mM. The operating tem­
perature of the process ranges from 400 ◦ C to 800 ◦ C. One of the sig­
nificant merit of MAP is rapid heating even the size of biomass is large.
Due to the higher heating value of MAP, the yield of bio-syngas and bio-
oil are higher than conventional process. MAP gained profound atten­
tion in recent years due to the bulky mass conversion, uniform heating,
easily controllable and non-agitation. Despite the above advantages the
application of microalgae on the MAP is limited due to poor absorption

Table 2
Elemental composition of biochar/bio-oil produced from microalgal and cyanobacterial biomasses.
Feedstock Process Type of product C H O N S Reference

Chlorella protothecoides Fast pyrolysis Bio-oil 62.07 8.76 11.24 9.74 – [31]
Spirulina Pyrolysis – 67.52 9.82 11.34 10.71 – [82]
Nannochloropsis – Bio-oil 80.2 6.2 5.81 6.2 [87]
Cyanobacteria – Bio-oil 67.58 8.95 14.48 7.75 [88]
Nannochloropsis Pyrolysis Biochar 55.34 1.96 37.54 5.16 [89]
Nannochloropsis Catalytic pyrolysis using MgCe/Al2O3 Biochar 57.01 2.13 36.23 4.63 – [89]
Isochrysis sp. Non catalytic pyrolysis Biochar 37.25 1.37 57.87 3.57 – [90]
Isochrysis sp. Catalytic pyrolysis using TiO2 Biochar 38.63 1.36 56.46 3.55 – [90]
Isochrysis sp. Non catalytic pyrolysis Bio-oil 66.70 8.14 17.53 7.63 – [90]

4
M. Sekar et al.
of microwave irradiation. To overcome the above limitation, the algae
are mixed with the absorber such as metallic oxides, activated carbons
and chars to achieve high temperature during the process [64,65]. For
illustration, addition of lignite char to the biomass enhances the tem­
perature significantly. Owing to the increase in the temperature, the
yield of bio-oil and bio-char increases. In regard of microwave power,
the huge increase in power is observed (390 to 700 MW). Meanwhile,
addition of 5% catalyst to the MAP process increases the yield of bio-fuel
up to 87%. Based on the target material moisture content and size of the
biomass the heating value of MAP differs. When the product has few
water polar molecules, no extra heating is required. In the other end, if
the product has excess water molecules then additional heat energy and
time is required. Similarly, spread of the radiation is uneven when
handling large biomass. Utilization of Chlorella sp. at 750 W and 480 ◦ C
reports 28% bio-oil yield. Increasing the temperature records higher gas
yield of 35% at 540 ◦ C and 1250 W power. The optimum conditions for
high bio-char yield were 362 ◦ C and 500 W (28%) [66–68]. Further,
addition of catalyst such as CaO, SiC and activated carbons increases the
total conversion of microalgae to the main product. However, the liquid
yield is lowered. Having said that, bio-char yield was 92.9 wt% which
signifies MAP is an effective process for the bio-char production. Hong
et al. carried out the pyrolysis of Spirulina, Chlorella and Porphyra with
catalyst SiC at various temperatures of 400, 500 and 700 ◦ C and cellu­
lose and ovalbumin are also applied as model compounds to trigger the
algal strains [69]. From the test, it is concluded that, the bio-oil yield
reached up to 24–29 wt% and the content of nitrogen increases. Mi­
crowave output, temperature, algae biomass affects the products yield.
Chen et al. evaluated the advantages of microwave assisted pyrolysis
using Chlorella vulgaris. They found addition of activated carbon and
silicon carbide increases the output main product due to deoxygenating
and aromatization [41]. Hu et al. demonstrated a study on the C. vulgaris
under different levels of microwave power conditions, catalyst, carbon
content and solid residues. At 1500 W and 2250 W, the maximum bio
yield was obtained. By controlling the microwave power levels pro­
duction of the bio-oil and bio-gas yield are increased 35.8% and 52.3%
respectively owing to the rise in maximum temperature. Besides, the
catalyst activated carbon promotes the pyrolysis of C. vulgaris [70]. In
the other hand, co-pyrolysis of the microalgae with polyvinyl chloride
(PVC) enhances the output yield of the biomass. Typically when the
power is increased from 800 W to 1000 W the yield rate of bio-oil was
profound. Further, use of the co-pyrolysis reduces the concentration of
aromatics on the oil and char with low heating value. Inclusion of the
optimum 30% of PVC increases the yield with reduction of nitrogenous
and oxygenous organic matter [71]. Furthermore, the content of the
aromatic hydrocarbon increased to 92.7% from 29.6% at 800 W. With
regard to the heating value significant raise were observed from 20 MJ/
kg to 30 MJ/kg [72,73]. Similar to co-pyrolysis, implantation of the
composite catalyst enables higher yield rate [74].
2.5. Hydropyrolysis
It is a special type of pyrolysis process where nitrogen is used as a
carrier gas. Further, the thermal decomposition occurs in the high
pressure hydrogen atmosphere. Compared to other processes, the pro­
duction of hydrocarbons is typically higher with improved structural
preservation. Usually this type of process typically used to produce bio-
oil with reduced oxygen content. However the yield rate depends on the
temperature. The optimized conditions for the maximum yield of bio-oil
and bio-gas are 310 ◦ C, 3 MPa and 60 min. The main products from the
hydropyrolysis oil were CH4, un-reacted H2, CO, and CO2 [75,76].
Further, addition of catalyst improves the production of HPO with
higher content of carbon and hydrogen. Meanwhile, the content of ox­
ygen and nitrogen is reduced. In addition, the heating value is improved
up to 39.63 MJ/kg. On the other hand, the deoxygenating and desul­
furization rates are promoted due to the influence of catalyst [77]. In­
clusion of catalyst CoMo and NiMo [78,79] at the optimized
5
Fuel 283 (2021) 119190
temperature and pressure of 450 ◦ C and 3.0–35.8 bar increased the
production yield. As the hydrogen pressure maintained below 15.9 bar,
there was an profound increase in the solid yield from 11.0 wt% to 15.7
wt% dry ash free basis. Besides, the oxygen content was controlled de­
pends on the requirement by controlling the pressure. Eventually they
predicted the feed of biomass at lower pressure are viable. On the con­
trary, the lifespan and workability of the catalyst will be affected as the
feed pressure is low. To overcome the shortcomings of low bio-oil
yielded in the pyrolysis process, fast hydropyrolysis was introduced.
Besides, addition of catalyst to the fast hyrdropyrolysis increases the
yield rate. Catalytic fast hydropyrolysis (CFHP) temperature and vapors
controlled by the second stage hydro processing [76,80,81]. Usage of the
two stage process produces 18 to 25 mol% higher carbon yield compared
to single stage pyrolysis.
3. Conclusion
Renewable energy production has become an inevitable research
avenue among the various countries to satiate the energy demand and
simultaneously reduce the emission of greenhouse gases from the
combustion of conventional fossil fuel. Renewable energies are many
viz., bioethanol, biobutanol, biodiesel, biogas, biohydrogen. In addition,
biochar, bio-oil, and syngas from thermochemical processing of algal
biomasses acquired much significance recently due to their application
in various refineries. In this case, pyrolysis method is widely used for the
production of biochar and bio-oil from microalgae and thus, the present
article provides insights on the different pyrolytic processes namely slow
pyrolysis, fast/flash pyrolysis, catalytic pyrolysis, microwave assisted
pyrolysis and hydropyrolys used for the conversion of various algal
biomass into biochar and bio-oil. To understand and select the pertinent
process for bio-oil production, the underlying mechanism for decom­
position of algal components into simpler products and then to fuel
production was detailed. However, an in-depth research attempts are
required to optimize pyrolytic processing conditions to select optimal
reaction parameters yielding higher bio-oil.
Declaration of Competing Interest
The authors declare that they have no known competing financial
interests or personal relationships that could have appeared to influence
the work reported in this paper.
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