Bioresource Technology 246 (2017) 2–11

Contents lists available at ScienceDirect

Bioresource Technology
journal homepage: www.elsevier.com/locate/biortech

Review

Recent developments on algal biochar production and characterization MARK

a a b c a
Kai Ling Yu , Beng Fye Lau , Pau Loke Show , Hwai Chyuan Ong , Tau Chuan Ling ,
⁎
Wei-Hsin Chend, Eng Poh Nge, Jo-Shu Changf,g,
a
Institute of Biological Sciences, Faculty of Science, University of Malaya, 50603 Kuala Lumpur, Malaysia
b
Bioseparation Research Group, Department of Chemical and Environmental Engineering, Faculty of Engineering, University of Nottingham Malaysia Campus, Jalan
Broga, 43500 Semenyih, Selangor Darul Ehsan, Malaysia
c
Department of Mechanical Engineering, Faculty of Engineering, University of Malaya, 50603 Kuala Lumpur, Malaysia
d
Department of Aeronautics and Astronautics, National Cheng Kung University, Tainan 701, Taiwan
e
School of Chemical Sciences, Universiti Sains Malaysia, USM, Malaysia
f
Department of Chemical Engineering, National Cheng Kung University, Tainan 701, Taiwan
g
Research Center for Energy Technology and Strategy, National Cheng Kung University, Tainan 701, Taiwan

G RA P H I C A L AB S T R A C T

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

Keywords: Algal biomass is known as a promising sustainable feedstock for the production of biofuels and other valuable
Algal biochar products. However, since last decade, massive amount of interests have turned to converting algal biomass into
Biochar synthesis biochar. Due to their high nutrient content and ion-exchange capacity, algal biochars can be used as soil
Biochar characterization amendment for agriculture purposes or adsorbents in wastewater treatment for the removal of organic or in-
Pyrolysis and torrefaction
organic pollutants. This review describes the conventional (e.g., slow and microwave-assisted pyrolysis) and
Thermochemical conversion
newly developed (e.g., hydrothermal carbonization and torrefaction) methods used for the synthesis of algae-
based biochars. The characterization of algal biochar and a comparison between algal biochar with biochar
produced from other feedstocks are also presented. This review aims to provide updated information on the
development of algal biochar in terms of the production methods and the characterization of its physical and
chemical properties to justify and to expand their potential applications.

1. Introduction
Renewable energy such as biomass is receiving more attention on its
applicability for sustainable supply to the environment (Al-Hamamre
et al., 2017). Algal biomass is considered as a promising feedstock due
to its wide distribution, rapid growth and high CO2 fixation efficiency
(Chen et al., 2015b; Roberts et al., 2015a). Growing algal biomass is a
distinctive way to sequester atmospheric carbon dioxide to minimize
greenhouse effect (Gronnow et al., 2013). A potential improvement on
conversion of biomass to biochar through thermochemical processes

⁎
Corresponding author at: Department of Chemical Engineering, National Cheng Kung University, Tainan 701, Taiwan.
E-mail address: changjs@mail.ncku.edu.tw (J.-S. Chang).

http://dx.doi.org/10.1016/j.biortech.2017.08.009
Received 11 June 2017; Received in revised form 2 August 2017; Accepted 3 August 2017
Available online 05 August 2017
0960-8524/ © 2017 Elsevier Ltd. All rights reserved.
K.L. Yu et al.
such as pyrolysis, hydrothermal carbonization or torrefaction is com-
mendable for further utilizing the algal biomass in the context of
biorefinery. Upgrading of current thermochemical processes is im-
portant to enhance the economic feasibility of biochar production
process with a faster rate, higher yield, and better quality for applica-
tions (e.g., higher value applications of biochars other than as fertilizer,
such as adsorbent for environmental pollutant uptake or bio-materials
for medical applications).
Biochar is a carbon-rich product of biomass produced by thermal
decomposition under limited oxygen (O2) supply at a relatively low
temperature (Alhashimi and Aktas, 2017; Chang et al., 2015). The
conversion of wet algal biomass into algal char can occur at a relatively
moderate thermal condition in a short time under batch processing
conditions (Heilmann et al., 2010). The composition of biochar varies
with the types of feedstock. For example, microalgal biochar consists of
large aggregates with irregular porosity. These features vary from the
structure of lignocellulose biochar produced after thermal decomposi-
tion treatment (Torri et al., 2011). Algal biochar has lower surface area
and carbon content, but higher cation exchange capacity compared to
lignocellulose biochar. The higher pH properties of algal biochar can
balance acidified soils, while the higher nutrient content of nitrogen,
ash and inorganic elements are beneficial for soil amendment in agri-
culture (Kołtowski et al., 2017; Sun et al., 2017).
In addition to soil amendment utilization, biochar can also be used
as a bio-adsorbent in water treatment to remediate organic/inorganic
contaminants due to its abundance of organic functional groups and
inorganic minerals (Awad et al., 2017; Johansson et al., 2016). How-
ever, selection of cheap raw bio-materials with better properties and
easy preparation steps of bio-adsorbent still present major challenges
for the application of biochar in the conventional wastewater treatment
(Inyang et al., 2016). Microalgae have been studied extensively as a
potential biosorbent for the removal of organic and inorganic pollutants
due to their biosorption capacity attributed by a large amount of
functional groups (Guo et al., 2016; Zeraatkar et al., 2016). Those
specific functional groups on microalgal biochar lead to some special
physic-chemical properties that could enhance its adsorption efficiency
for organic contaminants (Zheng et al., 2017). The biorefinery model of
microalgae that can produce valuable biofuels and biochar simulta-
neously making it an interesting approach for future research and de-
velopment. Therefore, this review aims to provide the latest develop-
ment of algae-based biochar production technology using
thermochemical processes such as pyrolysis, torrefaction and hydro-
thermal carbonization. This review also aims to provide updated in-
formation on the characterization of physical and chemical properties
of microalgal biochar to justify and to expand their potential applica-
tions. A future recommendation of research work related to algal bio-
char is also proposed in the review.
2. Algal biomass as the source for producing biofuels and biochar
Fig. 1 shows the schematic view of algal biomass production in
renewable energy and carbon sequestration. With the ability in nu-
trients uptake, algae possess a high growth rate and environmentally
tolerant characteristics to rapidly dominate in high nutrients environ-
ment. The high nutrient content of algae makes it a suitable feedstock
for biochar production for the potential use in soil amendment and
implement for long-term carbon sequestration. Algal biochar derived
from the remediation of wastewater could provide a notable benefit in
the future by utilizing biomass for carbon negative energy generation
and application to the environment (Bird et al., 2011). However, the
high nutrient content of algal biomass makes it a disadvantage in pyr-
olysis product distribution where more bio-oil product can be obtained.
One way to solve this problem is to extract the lipids from algae for bio-
oil production, while the residues are further used for biochar pro-
duction to the context of biorefinery (Wang et al., 2013). Algae have
been known as one of the promising sustainable energy feedstocks for
3
Bioresource Technology 246 (2017) 2–11
the future without the dependence on fossil fuels and their growth can
efficiently reduce emissions of greenhouse gases. Microalgae are pop-
ular choice for biofuel production since it is easy to cultivate them in a
large amount under various environments (Vassilev and Vassileva,
2016). All types of biofuels (i.e., solid, liquid and gas biofuels) can be
generated from microalgae using several conversion methods such as
direct combustion, chemical conversion, biochemical conversion and
thermochemical conversion. In addition to the success of algal tech-
nology in fuel production, other value-added co-products such as bio-
char can be produced simultaneously from algal feedstock for a bior-
efinery concept (Foley et al., 2011; Rashid et al., 2013).
Biochar is gaining more attention on its long term advantage in
carbon sequestration and application in agriculture for soil amendment
(Ennis et al., 2012). Biochar technology involved the CO2 uptake
through photosynthesis. The captured carbon undergoes conversion
processes such as pyrolysis to produce biochar with characteristic of
long-term carbon storage through soil amendment (Sohi et al., 2009).
Biochar production differs from other biomass energy production sys-
tems as this technology is carbon-negative. The International Biochar
Initiative (2008) estimated that biochar production has the potential of
mitigation of climate change by providing 3.67 Gt CO2 per year using
only biomass wastes. Biochar is potential to sequester up to 12% of
greenhouse gases from anthropogenic sources in ecologically and eco-
nomically sustainable systems (Ennis et al., 2012). Implementation of
biochar’s ability in mitigation of climate change at global scale is re-
cognized (Molina et al., 2009).
As a strategy to store captured carbon for a long time on impact to
greenhouse gas accumulation, biomass is converted into biochar that
has more than 90% carbon (Heilmann et al., 2010). Biochar derived
from microalgae is nutrient-rich (especially nitrogen-rich) so is well-
suited to serve as a fertilizer in agriculture soil (Torri et al., 2011). With
all the advantages of algal biochar, converting algal biomass into bio-
char can be economically feasible for algal production enterprise
(Bryant et al., 2012). However, to date there is still very limited lit-
erature regarding algal biochar and its utilization. This may markedly
hinder the future development and application of algae-based biochar
(Shukla et al., 2017), suggesting the need for a comprehensive litera-
ture review in this promising area.
3. Algal biochar production
Algal biomass is converted into biochar mainly through thermo-
chemical conversions, such as pyrolysis, hydrothermal carbonization
and torrefaction. The conventional way of synthesizing biochar is
through slow pyrolysis which gives a high char yield. Hydrothermal
carbonization produced a final carbonaceous material, which is also
denoted as hydrochar. Torrefaction is a pre-treatment method that has
been studied extensively to upgrade biomass into carbon-rich solid fuel
such as biochar (Chen et al., 2015d; Kumar et al., 2017). Details of
biochar synthesis methods are described as follows.
3.1. Conventional and microwave-assisted pyrolysis
Pyrolysis is one of the most promising technologies for converting
biomass into valuable biofuels as well as biochars. There are several
types of pyrolysis based on their operating conditions such as the
conventional slow pyrolysis, fast pyrolysis and also the latest developed
microwave-assisted pyrolysis. Each type of pyrolysis produces different
composition of solid, liquid and gaseous products according to their
operating parameters, such as temperature, heating rate and residence
time. Slow pyrolysis gives the highest yield of biochar while fast pyr-
olysis gives the highest yield of bio-oil with biochar as by-product (Roy
and Dias, 2017).
3.1.1. Conventional pyrolysis
Pyrolysis is the heating of biomass with the absence of oxygen or air
K.L. Yu et al.
Fig. 1. Algal biomass production for renewable energy production and carbon sequestration.
at a given rate typically at a temperature range of around 300–700 °C
(Chen et al., 2015c). The products obtained from pyrolysis are de-
termined by several factors, in particular the temperature and heating
rate (Basu, 2010). Biochar yield increases with a decrease in pyrolysis
temperature, an increase in the residence time, and a preferable low
heating rate. In addition, feedstock properties, such as moisture content
and particle size, also significantly affect the yield of biochar produced
via pyrolysis (Tripathi et al., 2016). Slow pyrolysis, the conventional
process in charcoal production, could yield the maximum amount of
biochar from biomass compared to other processes, such as fast pyr-
olysis and gasification (Chaiwong et al., 2012; Mohan et al., 2014). Up
to 50% of the carbon from biomass may be stored in the stable biochar
through pyrolysis (Bird et al., 2011). Biomass undergoes slow pyrolysis
process with a vapour residence time from several minutes to hours for
char production (Du, 2013). Vapours are restrained and reacted with
solid phase extensively for more char yield at the end of the process
(Mohan et al., 2014). Slow pyrolysis, in general, carried out at low
heating rates of 0.1–1 K/s with a residence time of around 450–550 s.
Pre-pyrolysis happens at the beginning, followed by solid decomposi-
tion corresponding to the high rate pyrolysis process to form pyrolysis
products. Decomposition of the char finally occurs at a very low rate
and carbon-rich biochar is formed (Suganya et al., 2016). Most of the
traditional slow pyrolysis used fixed bed reactors where heating is
provided by heated surface but there are studies that looked into al-
ternative heating methods such as microwave heating (Du, 2013; Wan
et al., 2009).
3.1.2. Microwave-assisted pyrolysis
Microwave-assisted pyrolysis is one of the most efficient thermo-
chemical processes in the production of biochar, bio-oil and syngas and
it has been successfully applied to plant residues such as wood and
sewage sludge (Lei et al., 2011). Some of the advantages of microwave
pyrolysis are high products yield, reduction of harmful chemical in bio-
oil, energy and cost-saving. Microwave technology uses electro-
magnetic waves to cause oscillation of material molecules and to pro-
duce heat. The technical advantages of microwave-assisted pyrolysis
over conventional pyrolysis are (1) uniform microwave heating that is
applicable on larger biomass particles, (2) production of higher heating
value syngas that can be used for in-situ electricity for microwave
generation, (3) cleaner products due to no agitation and fluidization in
the process, and (4) microwave heating is a mature technology with
scale-up feasibility (Du, 2013). There are some differences between
conventional slow pyrolysis and microwave-assisted pyrolysis in the
4
Bioresource Technology 246 (2017) 2–11
formation of biochar product. Conventional pyrolysis used typical
heating process, while microwave pyrolysis required some pre-treat-
ment and catalysts prior to heating. Moreover, in conventional pyr-
olysis, the pyrolysis gas is the by-product, while bio-oil, hot water and
non-condensable gases can be obtained after condensation of micro-
wave pyrolysis. There are numerous studies on the pyrolysis of lig-
nocellulosic biomass but reports on the production of algal biochar via
microwave heating are limited (Wan et al., 2009). Biochar that un-
dergoes further chemical or thermal processing after production can be
transformed into activated carbon (Spokas et al., 2011). However,
previous study mentioned that the decrease of functional groups in
biochar due to the release of volatiles during pyrolysis would result in a
challenge when using it as an adsorbent (Wang et al., 2015). Micro-
wave-assisted pyrolysis can be used in future scale-up production from
algal products into biochar for applications such as soil fertilizer due to
its economic production process. Previous reports on the algal biochar
production via the pyrolysis process are summarized in Table 1.
3.2. Torrefaction
Torrefaction is a thermochemical conversion process which is per-
formed under atmospheric pressure at the temperature between 200
and 300 °C under an inert condition in the absence of oxygen (Chen
et al., 2014a; Chen et al., 2015a). The process partly decomposes bio-
mass and produces a solid product (called torrefied biomass or char)
with high carbon content. A general sketch of torrefaction process in
algal biochar production is shown in Fig. 2. Torrefaction is used for
biofuel production from microalgae and its prime purpose is to produce
biochar (Bach et al., 2017b). Torrefaction is an emerging thermal bio-
mass pre-treatment process able to remove volatiles through different
decomposition reactions to reduce major limitations of biomass, up-
grade biomass quality and alter the combustion behaviour (Nhuchhen
et al., 2014). By altering the combustion behavior, fuel flexibility is
enhanced by making a wide range of fuels efficiently applicable in a co-
firing power plant. Torrefaction of microalgal biomass grown by using
flue gas from the thermal power plant can be made suitable for co-firing
in a pulverized coal power (Wu et al., 2012). The thermal pre-treatment
of torrefaction can be divided into dry and wet torrefaction, which is
also known as hydrothermal torrefaction or hydrothermal carboniza-
tion (Chen et al., 2015d; Yan et al., 2009). Hydrothermal carbonization
is to be discussed in Section 3.3. Comparison of the characteristics of
dry and wet torrefaction is shown in Table 2. The major advantage of
wet torrefaction over dry torrefaction is its ability to produce energy-
K.L. Yu et al. Bioresource Technology 246 (2017) 2–11

Table 1
The pyrolysis processes used for algal biochar production.

Types of process Biomass feedstock Temperature (°C) Biochar production References

Slow pyrolysis Chlorella-based algal residue 300–700 • 56.3% at 300 °C Chang et al. (2015)
• 66.2% at 500 °C
• 65.0% at 700 °C
• High concentration of nitrogen and other inorganic
elements
Slow pyrolysis Brown Laminaria japonica macroalgae 200–800 • 78.34% at 200 °C Jung et al. (2016)
• 63.64% at 400 °C
• 37.96% at 600 °C
• 27.05% at 800 °C
Fixed-bed pyrolysis Chlorella vulgaris 300–900 • 19.3–43.46% of biochar yield on different temperatures Yuan et al. (2015)
Fixed-bed pyrolysis Chlamydomonas reinhardtii 350 • Nitrogen-rich biochar Torri et al. (2011)
• Largest fraction in term of mass, 44 ± 1% w/w mass yield
of biochar
Fixed-bed pyrolysis Scenedesmus dimorphus 300–600 • when
Surface area of biochar increased from 1.72 to 123 m /g
temperature increased from 300-500 °C; reduced to
2
Bordoloi et al. (2016)

89 m2/g at 600 °C
• The recalcitrance of biochar increased from 0.62 to 0.76
with increasing temperature
Fixed-bed pyrolysis Seaweed 250–600 • Biochar
250 °C
energy yield of 61.50% at 600 °C to 93.95% at Tag et al. (2016)

Fixed-bed pyrolysis Green macroalgae Cladophora glomerata 400–600 • 4440 wt% yield at 400 °C Norouzi et al. (2016)
• 39 wt% yield at 500 °C
• 31%wt%of biochar
yield at 600 °C
Fluidized-bed fast Defatted Chlorella vulgaris 500 • Energy recoveryyield Wang et al. (2013)
pyrolysis • 94% of algal biomass in bio-oil and biochar is

• High inorganic biochar content

Fluidized-bed pyrolysis Laminaria digitata, Fucus serratus and mix 500 • 29–36% of biochar yield Yanik et al. (2013)
macroalgae species from Black sea • Production of biochar with lower heating value due to
higher ash content of 41–52%
Stepwise and non-
stepwise pyrolysis
Wastewater treatment high rate algal
pond (WWT HRAP) biomass
300–500 • High amount of biochar with more than 50 wt% of the
initial biomass was produced under both heating regimes
Mehrabadi et al.
(2016)
Microwave pyrolysis Macroalgae 240–400 • 54.8% of biochar yield Shuttleworth et al.
(2012)

dense product within a short residence time due to high heat transfer Table 2
rate in the aqueous media (Coronella et al., 2012; Hoekman et al., Comparison of the characteristics of dry and wet torrefaction (Yan et al., 2009).
2013). In wet torrefaction, microalgae are treated under hot com-
Characteristics Torrefaction
pressed water, producing a solid product that has high calorific value,
better hydrophobicity, and lower ash content (Bach et al., 2017b). Dry Wet (Hydrothermal)
Torrefaction could produce biochar with high calorific value or higher
Temperature 200–300 °C 180–260 °C
heating value so it can be used as an alternative feedstock for clean
Media Inert nitrogen gas Hot compressed water
energy production other than fossil fuel. The hydrophobicity of biochar Pressure Atmospheric pressure 200–700 psi
originating from the surface functional groups and the lower ash con- Residence time 80 min 5 min
tent are important properties, determining its effectiveness in applying Cooling process Flowing nitrogen; indirect Immerse into ice bath
as an adsorbent for pollutants uptake from soil and water. Bach et al. water cooling rapidly
Additional processes – Filtration and evaporation
(2017a) showed that, after wet torrefaction, at least 61.5% of energy in
Energy density Lower Higher
the microalgal biomass is retained. The calorific value intensified up to
21% and there is a decrease in the ash content of the microalgae.

Fig. 2. General torrefaction process for algal biochar production.

5
K.L. Yu et al.
Torrefaction is usually carried out at a low temperature and short re-
sidence time under low heating rate to give a higher yield of solid
product (Deng et al., 2009; Nhuchhen et al., 2014). Wu et al. (2012)
reported that the solid yield decreased when the torrefaction tem-
perature is increased. The effect of residence time on the mass yield of
torrefied biomass at 300 °C shows the mass yield decreased with an
increase in the residence time. The study concluded that temperature
influenced the mass yield more than residence time. Chen et al. (2014b)
shows the isothermal and non-isothermal torrefaction characteristics
and kinetics of a microalga Scenedesmus obliquus CNW-N. Microalgae
are classified based on the torrefaction temperature, light, mild and
severe torrefaction from the maximum decomposition rate and weight
loss. Non-isothermal torrefaction required intense pre-treatment than
the isothermal torrefaction. Pre-treatment severity is intensified by the
increasing of heating rate in non-isothermal torrefaction. Uemura et al.
(2015) reported the yields of solid, liquid and gas for a series of tor-
refaction temperature on a macroalga Laminaria japonica. The solid
yield decreased when the torrefaction temperature was increased. The
decrease in solid yield may be attributed to the decomposition of two
major components, alginate and mannitol in L. japonica. However, both
the liquid and gas yields increased when the temperature was increased
in conjunction with a decrease of solid yield with torrefaction tem-
perature. (Bach et al., 2017a) mentioned that the solid yield decreased
with an increase in temperature and residence time. The solid yield
decreased from 61.68% to 52.58% when the temperature was increased
from 160 °C to 180 °C. The solid yield decreased from 62.92% to
51.84% when the residence time increased from 5 min to 30 min. Chen
et al. (2016) showed that the solid yield of 51.3–93.9% in the torrefied
microalgae residue at the temperature ranged from 200 to 300 °C with a
residence time of 15–60 min. Previous study also shows the solid yield
of 50.8–95.7% in microalgae Chlamydomonas sp. JSC4 residue after
torrefaction at temperature 200–300 °C for 15–60 min. It is re-
commended that torrefaction of microalgae residue should be carried
out at an optimum temperature of 250 °C or below for less weight loss
and higher energy densification (Chen, 2015). The impact of torrefac-
tion upon biomass properties has been extensively investigated in the
last decade. However, there is limited literature on the study of algal
biochar from torrefaction process. As torrified algal biomass is a high
quality and environmental friendly solid product that may offer con-
siderable opportunities for worldwide greenhouse gas mitigation, fu-
ture research on this area is suggested.
3.3. Hydrothermal carbonization
Hydrothermal carbonization (HTC) is a new thermochemical tech-
nique that has gained more attention in the recent years due to its
environmental friendly and cost effectiveness (Erlach et al., 2012; Xiao
et al., 2012). HTC is a distinctive process that involves the conversion of
carbohydrate components of biomass into carbon-rich solids in water
Table 3
Algal hydrochar production using hydrothermal carbonization (HTC).
Biomass feedstock Temperature (°C) Reaction time
Microalgae
Dunaliella salina 190–210 30–120 min
Arthrospira platensis 190–210 2–4 h
Nannochloropsis sp. 180–220 15–30 min
Nannochloropsis oculata 180–215 15–45 min
Whole Spirulina 175–215 30 min
Lipid extracted Spirulina 175 30 min
Macroalgae
Sargassum horneri 180–210 2–16 h
Laminaria digitata 200–250 1h
Laminaria hyperborean 200–250 1h
Alaria esculenta 200–250 1h
6
Bioresource Technology 246 (2017) 2–11
where biochar is produced at lower temperatures (180–260 °C) and
elevated water or steam pressures (Libra et al., 2011; Titirici et al.,
2012). The process takes place in water under a self-generated pressures
being less than 10 bar with water as solvent (Titirici et al., 2012). This
process can be suitable for concentrating carbon of wet biomass where
no drying is required prior to pyrolysis, making it a potential alternative
for treatment of some waste streams (Brownsort, 2009). Char produced
from hydrothermal carbonization is called hydrochar (Libra et al.,
2011). HTC produce a higher product in a shorter period of time and
requires lower energy expense than conventional carbonization process
(Tekin et al., 2014). The advantages of the HTC process include (1)
required only low carbonization temperature, (2) can be synthesized in
the aqueous phase, (3) inexpensive process, (4) renewable materials
can be used as sources such as biomass and for the use of value-added
chemicals, such as nanoparticles in the structure (Kubo, 2013). Char
product obtained from HTC has the following properties: uniform
spherical particles; controlled porosity; functional surfaces (e.g., eOH,
eC]O, eCOOH); easily controlled surface chemistry and electronic
properties (Titirici et al., 2012).
In a hydrothermal process, biomass can be converted into valuable
products such as biochar, bio-oil and gaseous products by manipulating
process variables such as temperature, time of reaction, feedstock, the
presence of catalysts and pressure (Tekin et al., 2014). Temperature is
the most influential variable in the HTC process followed by residence
time and the types of feedstock (Nizamuddin et al., 2017). Lower
temperature tends to give a higher yield of solid product compared to
higher temperatures by affecting its physical and chemical character-
istics. At a higher temperature, the carbon content is higher whereas the
hydrogen and oxygen contents are lower. This results in a formation of
biochar with greater higher heating value (HHV). Char produced from
HTC of microalgae has a unique composition and with bituminous coal
quality (Heilmann et al., 2010). Process conditions were under a lower
temperature of 200 °C with 0.5 h of reaction time for effective carbo-
nization and production of algal char. The brief reaction time in the
batch process suggested the development of a continuous process for
HTC processing of algae. There are no specific catalytic agents that
significantly enhanced the carbonization process and/or increase the
yield of biochar. The most conceivable alternative pathway proposed in
the study was carbonization via a dehydration route. Previous literature
of algal hydrochar production in HTC is shown in Table 3. As there is
very limited literature on algal char production from the HTC process, it
would be an interesting topic for future studies. HTC process offers the
advantages of lowering the production cost and shortening the time
needed for the production of biochar. This can be achieved by utilizing
algal biomass residue and converting it into more valuable biofuels and
other products. HTC represents a feasible alternative way to convert
wet biomass into biochar by omitting the drying process.
Solid mass yield (%) References
25.3–45.7 Heilmann et al. (2010)
21.6–36.7 Yao et al. (2016)
30–47 Lu et al. (2014)
41–51 Levine et al. (2013)
23.3–49.3 Broch et al. (2014)
44.6 Broch et al. (2014)
32.7–52.3 Xu et al. (2013)
18.4–21.8 Smith and Ross (2016)
23.6–39.0 Smith and Ross (2016)
23.7–30.0 Smith and Ross (2016)
K.L. Yu et al. Bioresource Technology 246 (2017) 2–11

Table 4
Physical properties of biochars derived from microalgal and macroalgal biomass.

Feedstock Pyrolysis temperature and Biochar yield (%) HHV (MJ/kg) BET surface area References
duration (m2/g)

Microalgae
Arthrospira platensis 550 °C, 60 min 31.0 15.8 n.d. Chaiwong et al. (2012)
Arthrospira platensis 500 °C, 20 min 25.0 n.d. n.d. Conti et al. (2016)
Chlamydomonas reinhardtii 350 °C, 20 min 44.0 13.0 n.d. Torri et al. (2011)
Chlorella vulgaris 350 °C 31.0 23.0 n.d. Wang et al. (2013)
Cladophora sp. n.a. n.d. n.d. n.d. Maddi et al. (2011)
Desmodesmus communis 500 °C, 20 min 34.0 n.d. n.d. Conti et al. (2016)
Isochrysis sp. 500 °C, 1 h ∼30 7.56 n.d. Aysu et al. (2016)
Lyngbya sp. n.a. ∼20 16.4 n.d. Maddi et al. (2011)
Nannochloropsis sp. 400, 500, and 600 °C, 60 min 24.8–33.5 14.8 n.d. Aysu and Sanna (2015)
Spirogyra sp. 550 °C, 60 min 28.0 23.0 n.d. Chaiwong et al. (2012)
Tetraselmis sp. 500 °C, 1 h ∼20 10.37 n.d. Aysu et al. (2016)
Lacustrine alga 400, 500 and 600 °C, 45 min 41.3–48.3 n.d. n.d. Chiodo et al. (2016)
Mixed consortia 500, 600, and 800 °C, 1, 2, and 3 h 33.0–63.0 n.d. n.d. Sarkar et al. (2015)

Macroalgae
Ascophyllum nodosum Microwave assisted thermal 21.4 21.2 n.d. Yuan and Macquarrie
treatment (2015)
Cladophora sp. 550 °C, 60 min 31.0 16.7 n.d. Chaiwong et al. (2012)
Cladophora vagabunda 250–400 °C 67.0 n.d. 8.3 Bird et al. (2012)
Cladophora coelothrix Hydrothermal liquefaction 10.4 18.3 n.d. Neveux et al. (2014)
Cladophora vagabunda Hydrothermal liquefaction 18.7 15.1 n.d. Neveux et al. (2014)
Chaetomorpha linum Hydrothermal liquefaction 8.4 20.5 n.d. Neveux et al. (2014)
Derbesia tenuissima Hydrothermal liquefaction 8.1 9.1 n.d. Neveux et al. (2014)
Eucheuma sp. 450 °C, 60 min 57.2–61.7 14.6–17.2 30.0–34.8 Roberts et al. (2015b)
Gracilaria sp. 450 °C, 60 min 59.8–61.8 11.1–16.1 2.0–3.6 Roberts et al. (2015b)
Gracilaria gracilis 400, 500, and 600 °C n.d. 11.4 n.d. Francavilla et al. (2015)
Gracilaria gracilis residue 400, 500, and 600 °C 26–32 14.5 n.d. Francavilla et al. (2015)
Kappaphycus sp. 450 °C, 60 min 54.1–59.2 13.0–17.8 2.2–2.8 Roberts et al. (2015b)
Oedogonium sp. Hydrothermal liquefaction 10.2 5.2 n.d. Neveux et al. (2014)
Porphyra tenera 500 °C, 60 min n.d. n.d. n.d. Park et al. (2016)
Saccharina sp. 450 °C, 60 min 45.3–49.7 11.4–14.8 1.3–8.5 Roberts et al. (2015b)
Sargassum sp. 450 °C, 60 min 49.0–61.9 11.8–13.5 2.5–7.5 Roberts et al. (2015b)
Ulva flexuousa 300–500 °C, 60 min n.d. n.d. 1.2–4.3 Bird et al. (2011)
Ulva ohnoi Hydrothermal liquefaction 12.1 4.0 n.d. Neveux et al. (2014)
Undaria sp. 450 °C, 60 min 60.3–62.4 10.7–14.7 1.3–8.9 Roberts et al. (2015b)
Mixture of Cladophora coelothrix, Chaetomorpha 250–400 °C 74.5 n.d. n.d. Bird et al. (2012)
indica, Ulva flexuosa
Kelp n.a. n.d. n.d. 26.6 Boakye et al. (2016)
Spray-dried algae 300, 450, 600, and 750 °C, 10 and 19.3–72.8 8.2–9.2 14–19 Ronsse et al. (2013)
60 min

n.a., not available; n.d., not determined.

4. Algal biochar characterization
Characterization of the physical and chemical properties of algal
biochar is of great importance in determining their potential applica-
tions. The physical and chemical properties of biochar produced from
both microalgae and macroalgae are discussed as follows.
4.1. Physical properties of algal biochar
4.1.1. Biochar yield
Previous studies have demonstrated that algal samples could yield
relatively high amounts of biochar per unit biomass. However, com-
parative analysis of biochar derived from microalgae and macroalgae in
terms of their yields under similar experimental conditions is still
lacking. As shown in Table 4, the yield of biochar derived from micro-
and macroalgae (on a dry weight basis) ranged from 20.0 to 63.0% and
8.1–62.4%, respectively. There are attempts to investigate the factors
which affect the yield of algal biochar. Ronsse et al. (2013), for in-
stance, reported that the yield of algal biochar is lower than lig-
nocellulosic biomass, namely pine wood, wheat straw, and green waste.
The yield decreased when the pyrolysis temperature and residence time
were increased from 300 to 750 °C and from 10 to 60 min, respectively.
Similar results were also observed by Tag et al. (2016) who postulated
that such observations could be due to the differences in the chemical
components between algal and terrestrial biomass, particularly for the
composition of cell wall. Besides that, the high ash content in algal
samples might act catalytically during pyrolysis to alter the distribution
of products.
4.1.2. Higher heating value
The higher heating value (HHV) is the amount of heat released
when the sample (fuel) is combusted and the products have returned to
a temperature of 25 °C. It is typically measured using a bomb calori-
meter in the laboratory. As shown in Table 4, biochars derived from
microalgae (7.6–23.0 MJ/kg) and macroalgae (5.2–21.2 MJ/kg) have
comparable HHV. In general, the HHV of algal biochars is lower than
that of lignocellulosic biochars (which has been reported to exceed
30 MJ/kg), is likely attributed to a lower carbon content but higher ash
content in algal biomass.
4.1.3. Surface properties
The physical properties of biochars, such as their surface area,
porosity, and pore volume, are routinely analyzed. The Brunauer-
Emmet-Teller (BET) surface area of biochar can be estimated using a
surface area analyzer while a scanning electron microscope (SEM) can
be used to profile the surface topography and particle structure. The
surface area of algal biochar is generally low but some studies reported
that an increase in the pyrolysis temperature could result in a higher
surface area (Bird et al., 2011). Ronsse et al. (2013) found that the ash
content in the biomass is negatively correlated with the surface area of

7
K.L. Yu et al.
the resulting biochar. Wang et al. (2013) reported that the surface area
of biochar derived from C. vulgaris (2.4 m2/g) was deemed to be low
relative to biochar obtained from lignocellulosic biomass. Working with
biochar derived from macroalgae, Roberts et al. (2015b) reported that
biochar produced from the macroalgae Eucheuma sp. has a significantly
higher surface area (30.03–34.82 m2/g) than those of other species
which ranged from 1.29 to 8.87 m2/g.
Findings thus far have indicated that biochar derived from algal
samples has distinct structure and characteristics when compared with
the biomass before subjected to pyrolysis. For instance, Wang et al.
(2013) observed that the particles of biochar derived from a green
microalga, Chlorella vulgaris, are compact and irregular, and these are
different from the structure of the feedstock before pyrolysis. Similar
results were also reported for the biochar derived from Chlamydomonas
reinhardtii (Torri et al. (2011). These observations are in contrast with
biochars from lignocellulosic biomass, which normally retain their
feedstock’s structure. Table 4 summarizes the physical properties of
biochars derived from several microalgae and macroalgae species.
4.2. Chemical properties of algal biochar
4.2.1. Proximate and ultimate analysis
In proximate analysis, the moisture, volatile matter, ash, and fixed
carbon content of the samples are measured. Ultimate analysis (also
termed as elemental analysis), on the other hand, includes the de-
termination of carbon, hydrogen, nitrogen, sulphur, and oxygen within
the samples. As shown in Table 5, algal biochars are typically low in C
but high in N and minerals (ash) contents. The low C content, in
comparison to those derived from lignocellulosic biomass, is the char-
acteristic of biochars produced from micro- and macroalgae.
4.2.2. Inorganic elemental analysis
Inorganic mineral content of algal biochar is typically determined
using the inductively coupled plasma atomic emission spectrometry
(ICP-AES). Previous work has provided insights into the abundance of
various inorganic elements in algal biochar and enables comparison
with biochar derived from other feedstock. For example, Wang et al.
(2013) reported that biochar derived from C. vulgaris contained higher
concentrations of various trace elements, including P, K, Mg and Ca,
compared to biochar from lignocellulosic biomass. In a separate study,
biochars produced from both red and brown seaweeds have high con-
centrations of N (0.3–2.8%), P (0.5–6.6 g/kg), and K (5.1–119 g/kg)
(Roberts et al., 2015b). Results from both studies, when taken together,
seem to suggest that algal biochar has good prospects as fertilizers in
view of their mineral contents.
4.2.3. pH
As shown in Table 5, all algal biochar was found to be alkaline. The
pH of biochar derived from macroalgae ranges from 7.6 to 13.7,
whereas little information is available regarding those derived from
microalgae. The pH of biochar is found to be affected by the pyrolysis
temperature and the algal samples. According to the study by Ronsse
et al. (2013), the pH of biochar is correlated to the presence of oxygen
functionalities in the biochar. Tag et al. (2016) noted that the pH of
algal biochar (8.7–13.7) increased with an increase in the pyrolysis
temperature (250–600 °C). A plausible explanation is the increase in the
relative ash content in the biochar caused a rise in the pH of the biochar
especially under severe pyrolysis conditions (Ronsse et al., 2013)
4.2.4. Cation exchange capacity
The cation exchange capacity (CEC) of biochar is a measure of the
ability of biochar to adsorb cation nutrients. In other words, a biochar
with high CEC exerts beneficial effect by preventing nutrient leaching
in the soil. Roberts et al. (2015b) showed that seaweed biochar samples
have negligible or no exchangeable Al, but have high levels of the re-
maining exchangeable cations such as Ca, K, Mg and Na. In another
8
Bioresource Technology 246 (2017) 2–11
study by Tag et al. (2016), algal biochar produced at different pyrolysis
temperature was found to have higher CEC (25.6–52.6 cmol/kg) than
that produced from vine pruning (32.2–61.0 cmol/kg) and orange po-
mace (25.6–52.6 cmol/kg) under similar experimental conditions. As
CEC correlated with the ash content, it was suggested that the alkali and
earth alkali metals in biomass promoted the formation of O-containing
surface functional groups in the resulting biochar (Cely et al., 2015).
4.2.5. Functional groups
Fourier transform infrared spectroscopy (FTIR) spectral analysis is
used to identify the various functional groups in algal biochar. This
technique can be used to compare the chemical profiles of biochar
produced under different conditions, as well as between the raw bio-
mass and the resulting biochar. The latter is exemplified by the work of
Biswas et al. (2017) whereby FT-IR spectra demonstrated that, fol-
lowing hydrothermal liquefaction, the macromolecular crystal structure
of the algae was disrupted and products (biochar and bio-oil) were
formed. Table 5 summarizes the chemical properties of biochar derived
from some microalgae and macroalgae species.
4.3. Factors affecting the properties of algal biochar
In general, the method and temperature of pyrolysis are two im-
portant factors that determine the physical and chemical properties of
biochar (Jindo et al., 2014; Mukome et al., 2013). The operating con-
ditions such as heating rate, reaction vessel, chemical activation, re-
sidence time, and highest treatment temperature (HTT) also influence
the properties of biochar produced. The HHT is regarded to have the
greatest effect on the physical properties of biochar produced (Mukome
et al., 2013). In a recent study, Palanisamy et al. (2017) reported that
biochar of C. vulgaris prepared at higher temperatures (450–600 °C)
contained a higher proportion of organic matter (C, H and N) than those
produced at lower temperatures.
In addition, the type of feedstock used may affect the chemical
composition of the resulting biochar, such as the ash content, pH, H/C
ratio, surface area, as well as cation and anion exchange capabilities
(Sun et al., 2014; Tag et al., 2016). These factors are of great im-
portance when comes to the applications of biochar, particularly in the
agriculture sector. In a comparative analysis in the properties of biochar
produced by algae, grass, manure, wood, pomace, and nutshell, it was
found that feedstock is a better predictor of variation in the ash content
and C/N ratio of biochar than pyrolysis temperature (Mukome et al.,
2013). However, when one feedstock is being considered, pyrolysis
temperature is the best predictor for the surface area.
In terms of biochar production from algal species, the proportion
and composition of nutrients of algal-derived biochar is likely influ-
enced by a number of abiotic and biotic factors like species, habitat (e.g.
fresh, brackish or saline environment), and other factors. It is evidenced
by the findings of a number of researchers. Dealing with seaweed bio-
chars, Roberts et al. (2015b) found that biochars produced from red and
brown seaweeds have different elemental composition with biochars
from red seaweeds have higher concentrations of S and K and lower
concentrations of C and H than biochars produced from the brown
seaweeds. There are also variations in most physicochemical char-
acteristics of the biochar between species collected from different lo-
cations especially the cation exchange capability of the biochars. For
instance, the exchangeable K in Undaria sp. (13–420 cmol/kg) and
Kappaphycus sp. (26–210 cmol/kg) differed by an order of magnitude
depending on the location. Bird et al. (2012) also noted a difference in
the yield and ash content of the Chadophora vagabunda with their earlier
work (Bird et al., 2011). These may be attributed to moving to pilot
scale production with commercial pyrolysis equipment rather than
controlled laboratory production, purity of the materials collected in
the field, and lesser control over pyrolysis conditions.
K.L. Yu et al. Bioresource Technology 246 (2017) 2–11

Table 5
Chemical properties of biochars derived from microalgal and macroalgal biomass.

Biochar Proximate analysis (wt%) Ultimate analysis (wt%, dry ash-free) pH References

Moisture Volatile Ash Fixed carbon C H N S O

matter

Microalgae
Arthrospira platensis – 7.6 47.8 44.6 45.3 1.2 2.6 0.1 0.3 – Chaiwong et al. (2012)
Arthrospira platensis – – 47.8 – 45.3 1.2 2.6 – – – Chaiwong et al. (2013)
Arthrospira platensis – 28.0 29.5 42.0 51.0 2.5 7.7 – 18.0 – Conti et al. (2016)
Cladophora sp. – – – – 62.7 2.2 4.0 – 31.0 – Maddi et al. (2011)
Chlamydomonas – – 45.0 – 40.0 1.4 5.3 < 0.1 9.3 – Torri et al. (2011)
reinhardtii
Chlorella vulgaris 3.4 23.5 20.0 54.2 62.0 3.9 9.4 – 4.8 – Wang et al. (2013)
Desmodesmus communis – 22.0 36.8 41.0 51.0 3.0 7.0 0.1 14.0 – Conti et al. (2016)
Isochrysis sp. – – – – 43.5 1.5 3.7 – 51.3 – Aysu et al. (2016)
Lyngbya sp. – – – – 68.8 2.5 6.7 – 21.9 – Maddi et al. (2011)
Nannochloropsis sp. – – – – 55.3 2.0 5.2 – 37.5 – Aysu and Sanna (2015)
Spirogyra sp. – 16.8 23.5 59.7 62.4 0.4 2.1 0.5 4.1 – Chaiwong et al. (2012)
Tetraselmis sp. – – – – 48.1 1.7 4.3 – 46.0 – Aysu et al. (2016)
Lacustrine algae – – – – 27.0–30.5 0.8–1.1 0.7–1.3 – 67.1–71.5 10.05 Chiodo et al. (2016)

Macroalgae
Ascophyllum nodosum – – – – 51.1 5.3 1.9 – – – Yuan and Macquarrie
(2015)
Chaetomorpha indica – – 73.5 – 10.2 0.8 1.1 – – 7.8 Bird et al. (2011)
Chaetomorpha linum – – 16.0 – 23.6 1.3 2.4 – – 9.6 Bird et al. (2011)
Chaetomorpha linum – – – – 48.1 5.3 2.7 0.8 25.5 – Neveux et al. (2014)
Cladophora sp. – – – – 51.1 0.6 2.0 1.9 0.7 – Chaiwong et al. (2012)
Cladophora coelothrix – – – – 34.6 1.5 3.3 – – 8.7 Bird et al. (2011)
Cladophora coelothrix – – – – 44.2 4.1 3.7 1.7 20.1 – Neveux et al. (2014)
Cladophora patentiramea – – 47.0 – 20.3 1.2 1.7 – – 9.1 Bird et al. (2011)
Cladophora vagabunda – – 54.2 – 21.8 1.2 2.0 – – 9.9 Bird et al. (2011)
Cladophora vagabunda – – – – 36.1 3.9 2.6 0.3 20.6 – Neveux et al. (2014)
Cladophora patentiramea – – 47.0 – 20.3 1.2 1.7 – – 9.1 Bird et al. (2011)
Cladophoropsis sp. – – 46.5 – 23.6 1.5 2.8 – – 10.1 Bird et al. (2011)
Caulerpa taxifolia – – 20.9 – 24.8 1.2 2.4 – – 9.7 Bird et al. (2011)
Derbesia tenuissima – – – – 19.9 3.0 1.3 9.3 22.1 – Neveux et al. (2014)
Eucheuma sp. – – – – 23.7–25.6 1.2–1.8 0.7–0.8 7.0–9.3 20.6–24.9 8.2–8.6 Roberts et al. (2015b)
Gracilaria sp. – – – – 24.5–30.9 1.5–2.2 1.3–2.8 2.7–4.4 16.5–19.8 7.6–8.1 Roberts et al. (2015b)
Gracilaria gracilis 4.1 – 47.4 – 36.8 0.2 2.3 2.6 10.6 – Francavilla et al. (2015)
Gracilaria gracilis residue 5.4 – 30.7 – 41.2 2.2 2.3 1.3 22.3 – Francavilla et al. (2015)
Kappaphycus sp. – – – – 22.2–31.3 1.1–2.1 0.3–0.7 5.5–6.8 15.6–23.8 8.8–9.0 Roberts et al. (2015b)
Oedogonium sp. – – – – 12.2 1.4 1.2 0 6.6 – Neveux et al. (2014)
Porphyra tenera 5.5 – 21.3 73.2 74.7 3.0 9.1 4.2 9.0 – Park et al. (2016)
Saccharina sp. – – – – 28.0–35.0 1.9–2.4 2.2–2.4 1.0–1.6 16.4–18.4 11.0–11.2 Roberts et al. (2015b)
Sargassum sp. – – – – 28.9–29.1 2.0–2.1 1.0–1.1 0.9–2.8 15.3–18.2 10.1–10.8 Roberts et al. (2015b)
Ulva flexuousa – – 26.5–42.6 – 22.3–30.9 1.1–3.2 4.0–7.7 – – 8.0–10.1 Bird et al. (2011)
Ulva ohnoi – – – – 9.6 2.3 0.9 16.3 35.1 – Neveux et al. (2014)
Undaria sp. – – – – 27.3–34.8 1.7–2.8 2.3–2.4 0.6–0.8 14.1–15.6 9.9–10.9 Roberts et al. (2015b)
Mixture – 11.6–54.2 22.9–42.7 22.9–45.7 36.6–45.3 1.4–3.7 1.4–2.1 0–0.8 9.3–34.7 8.7–13.7 Tag et al. (2016)
Kelp – – – – 27.4 0.6 1.28 – 12.1 – Boakye et al. (2016)
Spray-dried algae – 3.9–70.0 46.3–76.4 30.0–96.1 62.7–90.6 1.4–7.2 – – – 4.9–12.5 Ronsse et al. (2013)

–: not determined.

4.4. Comparison of algal biochar with biochars derived from different
feedstocks
It is generally accepted that the first critical step in determining the
utility and applications of algal biochar is the quantification of the
properties of algal biochar and a comparison with biochar produced
from other commonly used terrestrial biomass feedstocks (Bird et al.,
2011). Studies thus far have pointed to the fact that biochars produced
from algal samples are fundamentally different from those produced
from lignocellulosic feedstock (Bird et al., 2012; Maddi et al., 2011). In
general, biochars produced from various algal species tend to have low
carbon content, surface area and cation exchange capability but high in
pH, nitrogen, and extractable inorganic nutrients including P, K, Ca and
Mg. In contrast, lignocellulosic materials-derived biochars tend to have
higher carbon contents and cation exchange capabilities with pH values
usually lower than 7, and significantly lower ash and available nutrient
contents (Jindo et al., 2014).
The difference in the chemical profiles between algal and other
lignocellulosic biochar gives important implications in their applica-
tions. The algal biochar is likely to provide significant direct nutrient
benefits to soils and crop productivity, and are likely to be particularly
useful for application on acidic soils. However, they are volumetrically
less able to provide the carbon sequestration benefits that can be pro-
vided with the high-carbon-content lignocellulosic biochars. Therefore,
Roberts et al. (2015b) proposed that a blending of seaweed and lig-
nocellulosic biochars could provide a soil ameliorant that combines a
high fixed C content with a mineral-rich substrate to enhance crop
productivity.
5. Future challenges and opportunities
Algal biochar could influence the global carbon sequestration on
mitigation of climate change from the production of energy to the ap-
plications in environmental management. In particular, the use of algal
biochar as biosorbents in wastewater treatment should be studied fur-
ther. Nevertheless, it is important to take note of some of the challenges

9
K.L. Yu et al.
that may lie ahead, such as cost effectiveness of the process and the fact
that wastewater contains various impurities that may interfere with the
process. In addition, production of algal biochar via the existing
methods could be further enhanced with microwave-assisted tech-
nology, whereas the additional energy consumption associated with the
microwave-assisted process should be well considered and minimized.
Microwave-assisted technology in the production of algal biochar is
indeed a promising approach that deserves more attention in the future.
Furthermore, optimization of algal biochar productivity can also be
achieved by employing a continuous process.
In terms of the algal biomass to be used for biochar production,
microalgae seem to be a more promising feedstock when compared to
macroalgae, in view of their advantages over the latter, such as their
rapid growth and the ease of cultivation and harvesting. Macroalgae, on
the other hand, require a larger area for cultivation and generally re-
quire a longer period of cultivation time. The quality and quantity of
macroalgal biomass are also greatly dependent on varieties of abiotic
and biotic factors. Moreover, microalgae are deemed to have higher
potential in biochar production due to their high nutrient contents
which are suitable for the use in agriculture. The recycling of microalgal
residue after biofuel production for a biorefinery concept is also fea-
sible. Taken together, future research on different aspects pertaining to
microalgal biochar, such as production methods and newer applica-
tions, is highly recommended in view of the scarcity of information on
these aspects.
6. Conclusions
Algal biomass as a third generation feedstock can be utilized in
biochar production in the context of biorefinery. Pyrolysis, torrefaction
or hydrothermal carbonization are suitable processes to produce algal
biochar of different composition and properties for varying further
applications. Microwave-assisted technology could be an interesting
approach in enhancing the current biochar production technologies.
Characterization of algal biochar is important for the understanding of
their chemical and physical properties, which are useful for de-
termining their potential applications (such as fertilizer for agricultural
purpose or adsorbent for water treatment). Development of algal bio-
char technologies is expected to contribute to a more sustainable en-
vironment in the future.
Acknowledgements
This study is supported by University of Malaya under the SATU
Joint Research Scheme (RU018J-2016, RU018L-2016, RU018O-2016
,RU018C-2016, ST001-2017, ST002-2017, ST003-2017, ST004-2017,
ST005-2017, ST006-2017 and RP031B-15AET). The financial support
from Taiwan’s Ministry of Science and Technology (MOST) under grant
numbers of MOST 106-3113-E-006-011, 106-3113-E-006-004-CC2,
104-2221-E-006-227-MY3, and 103-2221-E-006-190-MY3 is also
greatly appreciated.
References
Al-Hamamre, Z., Saidan, M., Hararah, M., Rawajfeh, K., Alkhasawneh, H.E., Al-Shannag,
M., 2017. Wastes and biomass materials as sustainable-renewable energy resources
for Jordan. Renew. Sustain. Energy Rev. 67, 295–314.
Alhashimi, H.A., Aktas, C.B., 2017. Life cycle environmental and economic performance
of biochar compared with activated carbon: a meta-analysis. Resour. Conserv. Recycl.
118, 13–26.
Awad, Y.M., Lee, S.-E., Ahmed, M.B.M., Vu, N.T., Farooq, M., Kim, I.S., Kim, H.S.,
Vithanage, M., Usman, A.R.A., Al-Wabel, M., Meers, E., Kwon, E.E., Ok, Y.S., 2017.
Biochar, a potential hydroponic growth substrate, enhances the nutritional status and
growth of leafy vegetables. J. Cleaner Prod. 156, 581–588.
Aysu, T., Abd Rahman, N.A., Sanna, A., 2016. Catalytic pyrolysis of Tetraselmis and
Isochrysis microalgae by nickel ceria based catalysts for hydrocarbon production.
Energy 103, 205–214.
Aysu, T., Sanna, A., 2015. Nannochloropsis algae pyrolysis with ceria-based catalysts for
production of high-quality bio-oils. Bioresour. Technol. 194, 108–116.
10
Bioresource Technology 246 (2017) 2–11
Bach, Q.-V., Chen, W.-H., Lin, S.-C., Sheen, H.-K., Chang, J.-S., 2017a. Wet torrefaction of
microalga Chlorella vulgaris ESP-31 with microwave-assisted heating. Energy
Convers. Manage. 141, 163–170.
Bach, Q.-V., Chen, W.-H., Sheen, H.-K., Chang, J.-S., 2017b. Gasification kinetics of raw
and wet-torrefied microalgae Chlorella vulgaris ESP-31 in carbon dioxide. Bioresour.
Technol.
Basu, P., 2010. Chapter 3 – Pyrolysis and torrefaction. In: Biomass Gasification and
Pyrolysis. Academic Press, Boston, pp. 65–96.
Bird, M.I., Wurster, C.M., de Paula Silva, P.H., Bass, A.M., de Nys, R., 2011. Algal biochar
– production and properties. Bioresour. Technol. 102 (2), 1886–1891.
Bird, M.I., Wurster, C.M., De Paula Silva, P.H., Paul, N.A., De Nys, R., 2012. Algal biochar:
effects and applications. GCB Bioenergy 4 (1), 61–69.
Biswas, B., Arun Kumar, A., Bisht, Y., Singh, R., Kumar, J., Bhaskar, T., 2017. Effects of
temperature and solvent on hydrothermal liquefaction of Sargassum tenerrimum
algae. Bioresour. Technol.
Boakye, P., Lee, C.W., Lee, W.M., Woo, S.H., 2016. The cell viability on kelp and fir
biochar and the effect on the field cultivation of corn. Clean Technol. 22 (1), 29–34.
Bordoloi, N., Narzari, R., Sut, D., Saikia, R., Chutia, R.S., Kataki, R., 2016.
Characterization of bio-oil and its sub-fractions from pyrolysis of Scenedesmus di-
morphus. Renewable Energy.
Broch, A., Jena, U., Hoekman, S., Langford, J., 2014. Analysis of solid and aqueous phase
products from hydrothermal carbonization of whole and lipid-extracted algae.
Energies 7 (1), 62.
Brownsort, P.A., 2009. Biomass Pyrolysis Processes: Review of Scope, Control and
Variability. UK Biochar Research Center, Edinburgh.
Bryant, H.L., Gogichaishvili, I., Anderson, D., Richardson, J.W., Sawyer, J., Wickersham,
T., Drewery, M.L., 2012. The value of post-extracted algae residue. Algal Res. 1 (2),
185–193.
Cely, P., Gascó, G., Paz-Ferreiro, J., Méndez, A., 2015. Agronomic properties of biochars
from different manure wastes. J. Anal. Appl. Pyrol. 111, 173–182.
Chaiwong, K., Kiatsiriroat, T., Vorayos, N., Thararax, C., 2012. Biochar production from
freshwater algae by slow pyrolysis. Maejo Int. J. Sci. Technol. 6 (2).
Chaiwong, K., Kiatsiriroat, T., Vorayos, N., Thararax, C., 2013. Study of bio-oil and bio-
char production from algae by slow pyrolysis. Biomass Bioenergy 56, 600–606.
Chang, Y.-M., Tsai, W.-T., Li, M.-H., 2015. Chemical characterization of char derived from
slow pyrolysis of microalgal residue. J. Anal. Appl. Pyrol. 111, 88–93.
Chen, W.-H., 2015. Microalgae oil: algae cultivation and harvest, algae residue torre-
faction and diesel engine emissions tests. Aerosol Air Qual. Res.
Chen, W.-H., Huang, M.-Y., Chang, J.-S., Chen, C.-Y., 2014a. Thermal decomposition
dynamics and severity of microalgae residues in torrefaction. Bioresour. Technol.
169, 258–264.
Chen, W.-H., Huang, M.-Y., Chang, J.-S., Chen, C.-Y., 2015a. Torrefaction operation and
optimization of microalga residue for energy densification and utilization. Appl.
Energy 154, 622–630.
Chen, W.-H., Huang, M.-Y., Chang, J.-S., Chen, C.-Y., Lee, W.-J., 2015b. An energy ana-
lysis of torrefaction for upgrading microalga residue as a solid fuel. Bioresour.
Technol. 185, 285–293.
Chen, W.-H., Lin, B.-J., Huang, M.-Y., Chang, J.-S., 2015c. Thermochemical conversion of
microalgal biomass into biofuels: a review. Bioresour. Technol. 184, 314–327.
Chen, W.-H., Peng, J., Bi, X.T., 2015d. A state-of-the-art review of biomass torrefaction,
densification and applications. Renew. Sustain. Energy Rev. 44, 847–866.
Chen, W.-H., Wu, Z.-Y., Chang, J.-S., 2014b. Isothermal and non-isothermal torrefaction
characteristics and kinetics of microalga Scenedesmus obliquus CNW-N. Bioresour.
Technol. 155, 245–251.
Chen, Y.-C., Chen, W.-H., Lin, B.-J., Chang, J.-S., Ong, H.C., 2016. Impact of torrefaction
on the composition, structure and reactivity of a microalga residue. Appl. Energy 181,
110–119.
Chiodo, V., Zafarana, G., Maisano, S., Freni, S., Urbani, F., 2016. Pyrolysis of different
biomass: direct comparison among Posidonia Oceanica, Lacustrine Alga and White-
Pine. Fuel 164, 220–227.
Conti, R., Fabbri, D., Vassura, I., Ferroni, L., 2016. Comparison of chemical and physical
indices of thermal stability of biochars from different biomass by analytical pyrolysis
and thermogravimetry. J. Anal. Appl. Pyrol. 122, 160–168.
Coronella, C.J., Yan, W., Reza, M.T., Vasquez, V.R., 2012. Method for Wet Torrefaction of
a Biomass. Google Patents.
Deng, J., Wang, G.-J., Kuang, J.-H., Zhang, Y.-L., Luo, Y.-H., 2009. Pretreatment of
agricultural residues for co-gasification via torrefaction. J. Anal. Appl. Pyrol. 86 (2),
331–337.
Du, Z., 2013. Thermochemical Conversion of Microalgae for Biofuel Production.
University of Minnesota.
Ennis, C.J., Evans, A.G., Islam, M., Ralebitso-Senior, T.K., Senior, E., 2012. Biochar:
carbon sequestration, land remediation, and impacts on soil microbiology. Crit. Rev.
Environ. Sci. Technol. 42 (22), 2311–2364.
Erlach, B., Harder, B., Tsatsaronis, G., 2012. Combined hydrothermal carbonization and
gasification of biomass with carbon capture. Energy 45 (1), 329–338.
Foley, P.M., Beach, E.S., Zimmerman, J.B., 2011. Algae as a source of renewable che-
micals: opportunities and challenges. Green Chem. 13 (6), 1399–1405.
Francavilla, M., Manara, P., Kamaterou, P., Monteleone, M., Zabaniotou, A., 2015.
Cascade approach of red macroalgae Gracilaria gracilis sustainable valorization by
extraction of phycobiliproteins and pyrolysis of residue. Bioresour. Technol. 184,
305–313.
Gronnow, M.J., Budarin, V.L., Mašek, O., Crombie, K.N., Brownsort, P.A., Shuttleworth,
P.S., Hurst, P.R., Clark, J.H., 2013. Torrefaction/biochar production by microwave
and conventional slow pyrolysis–comparison of energy properties. GCB Bioenergy 5
(2), 144–152.
Guo, W.-Q., Zheng, H.-S., Li, S., Du, J.-S., Feng, X.-C., Yin, R.-L., Wu, Q.-L., Ren, N.-Q.,
K.L. Yu et al.
Chang, J.-S., 2016. Removal of cephalosporin antibiotics 7-ACA from wastewater
during the cultivation of lipid-accumulating microalgae. Bioresour. Technol. 221,
284–290.
Heilmann, S.M., Davis, H.T., Jader, L.R., Lefebvre, P.A., Sadowsky, M.J., Schendel, F.J.,
Von Keitz, M.G., Valentas, K.J., 2010. Hydrothermal carbonization of microalgae.
Biomass Bioenergy 34 (6), 875–882.
Hoekman, S.K., Broch, A., Robbins, C., Zielinska, B., Felix, L., 2013. Hydrothermal car-
bonization (HTC) of selected woody and herbaceous biomass feedstocks. Biomass
Convers. Biorefin. 3 (2), 113–126.
Inyang, M.I., Gao, B., Yao, Y., Xue, Y., Zimmerman, A., Mosa, A., Pullammanappallil, P.,
Ok, Y.S., Cao, X., 2016. A review of biochar as a low-cost adsorbent for aqueous
heavy metal removal. Crit. Rev. Environ. Sci. Technol. 46 (4), 406–433.
Jindo, K., Mizumoto, H., Sawada, Y., Sanchez-Monedero, M.A., Sonoki, T., 2014. Physical
and chemical characterization of biochars derived from different agricultural re-
sidues. Biogeosciences 11 (23), 6613–6621.
Johansson, C.L., Paul, N.A., de Nys, R., Roberts, D.A., 2016. Simultaneous biosorption of
selenium, arsenic and molybdenum with modified algal-based biochars. J. Environ.
Manage. 165, 117–123.
Jung, K.-W., Jeong, T.-U., Kang, H.-J., Ahn, K.-H., 2016. Characteristics of biochar de-
rived from marine macroalgae and fabrication of granular biochar by entrapment in
calcium-alginate beads for phosphate removal from aqueous solution. Bioresour.
Technol. 211, 108–116.
Kołtowski, M., Charmas, B., Skubiszewska-Zięba, J., Oleszczuk, P., 2017. Effect of biochar
activation by different methods on toxicity of soil contaminated by industrial activity.
Ecotoxicol. Environ. Saf. 136, 119–125.
Kubo, S., 2013. Nanostructured carbohydrate–derived carbonaceous materials. TANSO
2013 (258), 232–233.
Kumar, G., Shobana, S., Chen, W.-H., Bach, Q.-V., Kim, S.-H., Atabani, A.E., Chang, J.-S.,
2017. A review of thermochemical conversion of microalgal biomass for biofuels:
chemistry and processes. Green Chem. 19 (1), 44–67.
Lei, H., Ren, S., Wang, L., Bu, Q., Julson, J., Holladay, J., Ruan, R., 2011. Microwave
pyrolysis of distillers dried grain with solubles (DDGS) for biofuel production.
Bioresour. Technol. 102 (10), 6208–6213.
Levine, R.B., Sierra, C.O.S., Hockstad, R., Obeid, W., Hatcher, P.G., Savage, P.E., 2013.
The use of hydrothermal carbonization to recycle nutrients in algal biofuel produc-
tion. Environ. Prog. Sustainable Energy 32 (4), 962–975.
Libra, J.A., Ro, K.S., Kammann, C., Funke, A., Berge, N.D., Neubauer, Y., Titirici, M.-M.,
Fühner, C., Bens, O., Kern, J., 2011. Hydrothermal carbonization of biomass re-
siduals: a comparative review of the chemistry, processes and applications of wet and
dry pyrolysis. Biofuels 2 (1), 71–106.
Lu, Y., Levine, R.B., Savage, P.E., 2014. Fatty acids for nutraceuticals and biofuels from
hydrothermal carbonization of microalgae. Ind. Eng. Chem. Res. 54 (16), 4066–4071.
Maddi, B., Viamajala, S., Varanasi, S., 2011. Comparative study of pyrolysis of algal
biomass from natural lake blooms with lignocellulosic biomass. Bioresour. Technol.
102 (23), 11018–11026.
Mehrabadi, A., Craggs, R., Farid, M.M., 2016. Pyrolysis of wastewater treatment high rate
algal pond (WWT HRAP) biomass. Algal Res.
Mohan, D., Sarswat, A., Ok, Y.S., Pittman, C.U., 2014. Organic and inorganic con-
taminants removal from water with biochar, a renewable, low cost and sustainable
adsorbent–a critical review. Bioresour. Technol. 160, 191–202.
Molina, M., Zaelke, D., Sarma, K.M., Andersen, S.O., Ramanathan, V., Kaniaru, D., 2009.
Reducing abrupt climate change risk using the Montreal Protocol and other reg-
ulatory actions to complement cuts in CO2 emissions. Proc. Natl. Acad. Sci. U.S.A.
106 (49), 20616–20621.
Mukome, F.N., Zhang, X., Silva, L.C., Six, J., Parikh, S.J., 2013. Use of chemical and
physical characteristics to investigate trends in biochar feedstocks. J. Agric. Food
Chem. 61 (9), 2196–2204.
Neveux, N., Yuen, A.K., Jazrawi, C., Magnusson, M., Haynes, B.S., Masters, A.F., Montoya,
A., Paul, N.A., Maschmeyer, T., de Nys, R., 2014. Biocrude yield and productivity
from the hydrothermal liquefaction of marine and freshwater green macroalgae.
Bioresour. Technol. 155, 334–341.
Nhuchhen, D.R., Basu, P., Acharya, B., 2014. A comprehensive review on biomass tor-
refaction. Int. J. Renew. Energy Biofuels 2014, 1–56.
Nizamuddin, S., Baloch, H.A., Griffin, G., Mubarak, N., Bhutto, A.W., Abro, R., Mazari,
S.A., Ali, B.S., 2017. An overview of effect of process parameters on hydrothermal
carbonization of biomass. Renew. Sustain. Energy Rev. 73, 1289–1299.
Norouzi, O., Jafarian, S., Safari, F., Tavasoli, A., Nejati, B., 2016. Promotion of hydrogen-
rich gas and phenolic-rich bio-oil production from green macroalgae Cladophora
glomerata via pyrolysis over its bio-char. Bioresour. Technol. 219, 643–651.
Palanisamy, M., Mukund, S., Sivakumar, U., Sivasubramanian, Karthikeyan, V., 2017.
Bio-char production from micro algal biomass of Chlorella vulgaris. PHYKOS 47 (1),
99–104.
Park, S.H., Cho, H.J., Ryu, C., Park, Y.-K., 2016. Removal of copper (II) in aqueous so-
lution using pyrolytic biochars derived from red macroalga Porphyra tenera. J. Ind.
Eng. Chem. 36, 314–319.
Rashid, N., Rehman, M.S.U., Han, J.-I., 2013. Recycling and reuse of spent microalgal
biomass for sustainable biofuels. Biochem. Eng. J. 75, 101–107.
Roberts, D.A., Cole, A.J., Paul, N.A., de Nys, R., 2015a. Algal biochar enhances the re-
vegetation of stockpiled mine soils with native grass. J. Environ. Manage. 161,
173–180.
Roberts, D.A., Paul, N.A., Dworjanyn, S.A., Bird, M.I., de Nys, R., 2015b. Biochar from
commercially cultivated seaweed for soil amelioration. Sci. Rep. 5, 9665.
Ronsse, F., van Hecke, S., Dickinson, D., Prins, W., 2013. Production and characterization
11
Bioresource Technology 246 (2017) 2–11
of slow pyrolysis biochar: influence of feedstock type and pyrolysis conditions. GCB
Bioenergy 5 (2), 104–115.
Roy, P., Dias, G., 2017. Prospects for pyrolysis technologies in the bioenergy sector: a
review. Renew. Sustain. Energy Rev. 77, 59–69.
Sarkar, O., Agarwal, M., Naresh Kumar, A., Venkata Mohan, S., 2015. Retrofitting he-
trotrophically cultivated algae biomass as pyrolytic feedstock for biogas, bio-char and
bio-oil production encompassing biorefinery. Bioresour. Technol. 178, 132–138.
Shukla, S., Gita, S., Bharti, V., Bhuvaneswari, G., Wikramasinghe, W., 2017. Atmospheric
Carbon Sequestration Through Microalgae: Status, Prospects, and Challenges. In:
Agro-Environmental Sustainability. Springer, pp. 219–235.
Shuttleworth, P., Budarin, V., Gronnow, M., Clark, J.H., Luque, R., 2012. Low tempera-
ture microwave-assisted vs conventional pyrolysis of various biomass feedstocks. J.
Nat. Gas Chem. 21 (3), 270–274.
Smith, A.M., Ross, A.B., 2016. Production of bio-coal, bio-methane and fertilizer from
seaweed via hydrothermal carbonisation. Algal Res. 16, 1–11.
Sohi, S., Loez-Capel, E., Krull, E., Bol, R., 2009. Biochar’s roles in soil and climate change:
a review of research needs. CSIRO Land Water Sci. Rep. 5 (09), 1–57.
Spokas, K.A., Novak, J.M., Stewart, C.E., Cantrell, K.B., Uchimiya, M., DuSaire, M.G., Ro,
K.S., 2011. Qualitative analysis of volatile organic compounds on biochar.
Chemosphere 85 (5), 869–882.
Suganya, T., Varman, M., Masjuki, H., Renganathan, S., 2016. Macroalgae and microalgae
as a potential source for commercial applications along with biofuels production: a
biorefinery approach. Renew. Sustain. Energy Rev. 55, 909–941.
Sun, H., Lu, H., Chu, L., Shao, H., Shi, W., 2017. Biochar applied with appropriate rates
can reduce N leaching, keep N retention and not increase NH3 volatilization in a
coastal saline soil. Sci. Total Environ. 575, 820–825.
Sun, Y., Gao, B., Yao, Y., Fang, J., Zhang, M., Zhou, Y., Chen, H., Yang, L., 2014. Effects of
feedstock type, production method, and pyrolysis temperature on biochar and hy-
drochar properties. Chem. Eng. J. 240, 574–578.
Tag, A.T., Duman, G., Ucar, S., Yanik, J., 2016. Effects of feedstock type and pyrolysis
temperature on potential applications of biochar. J. Anal. Appl. Pyrol. 120, 200–206.
Tekin, K., Karagöz, S., Bektaş, S., 2014. A review of hydrothermal biomass processing.
Renew. Sustain. Energy Rev. 40, 673–687.
Titirici, M.-M., White, R.J., Falco, C., Sevilla, M., 2012. Black perspectives for a green
future: hydrothermal carbons for environment protection and energy storage. Energy
Environ. Sci. 5 (5), 6796–6822.
Torri, C., Samorì, C., Adamiano, A., Fabbri, D., Faraloni, C., Torzillo, G., 2011.
Preliminary investigation on the production of fuels and bio-char from
Chlamydomonas reinhardtii biomass residue after bio-hydrogen production.
Bioresour. Technol. 102 (18), 8707–8713.
Tripathi, M., Sahu, J.N., Ganesan, P., 2016. Effect of process parameters on production of
biochar from biomass waste through pyrolysis: a review. Renew. Sustain. Energy Rev.
55, 467–481.
Uemura, Y., Matsumoto, R., Saadon, S., Matsumura, Y., 2015. A study on torrefaction of
Laminaria japonica. Fuel Process. Technol. 138, 133–138.
Vassilev, S.V., Vassileva, C.G., 2016. Composition, properties and challenges of algae
biomass for biofuel application: an overview. Fuel 181, 1–33.
Wan, Y., Chen, P., Zhang, B., Yang, C., Liu, Y., Lin, X., Ruan, R., 2009. Microwave-assisted
pyrolysis of biomass: catalysts to improve product selectivity. J. Anal. Appl. Pyrol. 86
(1), 161–167.
Wang, K., Brown, R.C., Homsy, S., Martinez, L., Sidhu, S.S., 2013. Fast pyrolysis of mi-
croalgae remnants in a fluidized bed reactor for bio-oil and biochar production.
Bioresour. Technol. 127, 494–499.
Wang, N., Tahmasebi, A., Yu, J., Xu, J., Huang, F., Mamaeva, A., 2015. A Comparative
study of microwave-induced pyrolysis of lignocellulosic and algal biomass. Bioresour.
Technol. 190, 89–96.
Wu, K.-T., Tsai, C.-J., Chen, C.-S., Chen, H.-W., 2012. The characteristics of torrefied
microalgae. Appl. Energy 100, 52–57.
Xiao, L.-P., Shi, Z.-J., Xu, F., Sun, R.-C., 2012. Hydrothermal carbonization of lig-
nocellulosic biomass. Bioresour. Technol. 118, 619–623.
Xu, Q., Qian, Q., Quek, A., Ai, N., Zeng, G., Wang, J., 2013. Hydrothermal carbonization
of macroalgae and the effects of experimental parameters on the properties of hy-
drochars. ACS Sustain. Chem. Eng. 1 (9), 1092–1101.
Yan, W., Acharjee, T.C., Coronella, C.J., Vásquez, V.R., 2009. Thermal pretreatment of
lignocellulosic biomass. Environ. Prog. Sustain. Energy 28 (3), 435–440.
Yanik, J., Stahl, R., Troeger, N., Sinag, A., 2013. Pyrolysis of algal biomass. J. Anal. Appl.
Pyrol. 103, 134–141.
Yao, C., Wu, P., Pan, Y., Lu, H., Chi, L., Meng, Y., Cao, X., Xue, S., Yang, X., 2016.
Evaluation of the integrated hydrothermal carbonization-algal cultivation process for
enhanced nitrogen utilization in Arthrospira platensis production. Bioresour.
Technol. 216, 381–390.
Yuan, T., Tahmasebi, A., Yu, J., 2015. Comparative study on pyrolysis of lignocellulosic
and algal biomass using a thermogravimetric and a fixed-bed reactor. Bioresour.
Technol. 175, 333–341.
Yuan, Y., Macquarrie, D.J., 2015. Microwave assisted step-by-step process for the pro-
duction of fucoidan, alginate sodium, sugars and biochar from Ascophyllum nodosum
through a biorefinery concept. Bioresour. Technol. 198, 819–827.
Zeraatkar, A.K., Ahmadzadeh, H., Talebi, A.F., Moheimani, N.R., McHenry, M.P., 2016.
Potential use of algae for heavy metal bioremediation, a critical review. J. Environ.
Manag. 181, 817–831.
Zheng, H., Guo, W., Li, S., Chen, Y., Wu, Q., Feng, X., Yin, R., Ho, S.-H., Ren, N., Chang, J.-
S., 2017. Adsorption of p-nitrophenols (PNP) on microalgal biochar: analysis of high
adsorption capacity and mechanism. Bioresour. Technol.