Algal Research 51 (2020) 102031

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Algal Research
journal homepage: www.elsevier.com/locate/algal

Microalgae pyrolysis under isothermal and non-isothermal conditions T

Eduardo Cano-Pleite , Mariano Rubio-Rubio, Néstor García-Hernando, Antonio Soria-Verdugo
⁎

Carlos III University of Madrid (Spain), Thermal and Fluids Engineering Department, Avda. de la Universidad 30, 28911 Leganés, Madrid, Spain

ARTICLE INFO ABSTRACT

Keywords: The present work analyzes and compares the non-isothermal and isothermal pyrolysis processes of two different
Chlorella pyrenoidosa kinds of microalgae: Spirulina platensis and Chlorella pyrenoidosa. The non-isothermal pyrolysis process is carried
Spirulina platensis out in a Thermogravimetric Analyzer (TGA), whereas a macro-TGA bubbling fluidized bed reactor is used for the
Fluidized bed isothermal pyrolysis reaction. The simplified Distributed Activation Energy Model (DAEM) is employed to derive
Microalgae
the kinetic parameters of the reaction in the TGA, i.e., the pre-exponential factor and the activation energy. A
Pyrolysis kinetics
Thermogravimetric analysis
consecutive reaction, first-order pyrolysis model with three competitive pseudo-components for the released
pyrolysis vapors is proposed to evaluate the isothermal pyrolysis experiments conducted in a macro-TGA bub­
bling fluidized bed. The fluidized bed experimental setup allows measuring the real-time mass evolution during
the microalgae pyrolysis process, which could be used to obtain the kinetic parameters of the different reactions
of which the consecutive reaction model is comprised. The activation energies of the reactions using this iso­
thermal pyrolysis model are in good agreement, both qualitatively and quantitatively, with those obtained from
the non-isothermal pyrolysis measurements run in the TGA. A quantitative comparison reveals that the TGA
measurements could be employed to provide a useful first estimation of the activation energy of the isothermal
pyrolysis process in the bubbling fluidized bed. Qualitatively, the Differential Thermogravimetric (DTG) curves
obtained from the thermogravimetric analysis revealed the presence of three peaks in the Chlorella pyrenoidosa
DTG curve and two peaks in the Spirulina platensis DTG curve, which is in agreement with the number of pseudo-
component reactions in the isothermal pyrolysis model. This indicates the capability of the non-isothermal
pyrolysis tests in a TGA to predict the number of reactions required to characterize the isothermal pyrolysis
process.

1. Introduction
Bio-fuels production has been traditionally based on edible biomass
and non-food energy crops, corresponding to the first and second
generation of bio-fuels, respectively. A high conversion efficiency can
be attained for first-generation bio-fuels. However, the use of edible
biomass for energy purposes resulted in social and political controversy
[1] since this can lead to shortage of food, especially in underdeveloped
and developing countries. Second-generation bio-fuels are character­
ized by a lower conversion efficiency. Thus, they are not economically
profitable, and their industrial production requires a huge extension of
arable land, leading again to controversy due to the competition of
edible and non-food crops for arable land [2]. The problem derived
from the first- and second-generation of bio-fuels can be solved by the
third-generation bio-fuels, which are based on aquatic crops, e.g., algae
and microalgae. The use of microalgae as feedstock for bio-fuel gen­
eration has various advantages, such as their fast-growing capability
[3], their higher photosynthesis efficiency compared to terrestrial crops
[4], and their capacity to grow in non-arable land and even in waste­
water [5]. Microalgae are composed of three main pseudo-components,
namely proteins, carbohydrates and lipids. In short, proteins are mac­
romolecules made up of monomers in polymerized chains, carbohy­
drates are sugar monomers or polysaccharides such as glucose, cellulose
and starch, and lipids are long hydrocarbon chains attached with car­
boxyl functional groups [6].
Several techniques have been used to obtain liquid bio-fuels from
microalgae due to their potential superior properties compared to lig­
nocellulosic and waste biomass. The most widely used conversion
techniques, operating with either dry or wet microalgae, are algal lipid
extraction and upgrading (ALU) and hydrothermal liquefaction (HTL)
[7,8]. In contrast, high-quality bio-fuels can be also obtained from
pyrolysis of dry microalgae [9]. Pyrolysis consists in the thermal de­
gradation of a solid fuel in absence of oxygen, obtaining a solid residue
(biochar), liquid products (bio-oil), and gas products (permanent gas).
The amount and quality of each yield obtained from pyrolysis depends
on the operating conditions of the process, i.e., reactor temperature,

⁎
Corresponding author.
E-mail address: edcanop@ing.uc3m.es (E. Cano-Pleite).

https://doi.org/10.1016/j.algal.2020.102031
Received 8 May 2020; Received in revised form 29 July 2020; Accepted 29 July 2020
Available online 14 August 2020
2211-9264/ © 2020 Elsevier B.V. All rights reserved.
E. Cano-Pleite, et al.
Nomenclature
A pre-exponential factor [s−1]
α degree of conversion [%]
β heating rate [K min−1]
E activation energy [kJ/mol]
k rate coefficient [s−1]
m mass of the sample remaining [g]
m0 initial mass of the sample [g]
R universal gas constant [J mol−1 K−1]
t time [min]
T temperature [°C, K]
Tb bed temperature [°C]
X percentage of remaining mass of the sample [%]
XSR percentage of solid residue generated [%]
biomass heating rate, residence time of pyrolysis vapors, biomass par­
ticle size, biomass feeding rate, and reaction time [10].
The kinetics of microalgae pyrolysis based on Thermogravimetric
Analyzer (TGA) measurements was deeply reviewed by Bach and Chen
[11]. In their work, they provided a state-of-the-art revision on the
pyrolysis kinetics of various microalgae, where different models, in­
cluding single reaction and distributed activation energy models, are
analyzed and discussed. The pyrolysis of microalgae has been widely
studied in the literature for many species using different modeling
strategies [12]. For instance, the Vyazovkin method was applied by Gai
et al. [13] to analyze the pyrolysis of Chlorella pyrenoidosa and Spirulina
platensis. The Kissinger method was used to study the pyrolysis of
Nannochloropsis oculata [14], periphytic microalgae [15] and the salt-
water cord grass Spartina alterniflora [16]. A multiple-step model was
used for the analysis of Chlorella vulgaris, Scenedesmus almeriensis and
Nannochloropsis gaditana [17]. The simplified Distributed Activation
Energy Model (DAEM) has been extensively employed in the research of
several microalgae species, such as Chlorella pyrenoidosa [18], Chlorella
sorokiniana [19], Monoraphidium [19], Chlorella humicola [20], Chlorella
vulgaris [21], Nannochloropsis oculata [22], and Tetraselmis sp. [22].
Even though there exist many kinetic studies in the literature analyzing
the pyrolysis process of microalgae based on TGA measurements, stu­
dies comparing TGA measurements with pyrolysis in other reactors,
such as fixed or fluidized beds, are scarce.
The biomass conversion rate during pyrolysis depends on the re­
actor design, for which a deep understanding of the chemical kinetics of
the process is required. In this sense, non-isothermal pyrolysis mea­
surements conducted in thermogravimetric analyzers have been widely
used to derive the biomass kinetic parameters of the pyrolysis process.
Various kinetic models have been developed to describe the pyrolysis of
biomass, including the single reaction model, multiple parallel reac­
tions models, series reaction or consecutive reaction models, iso­
conversional models or the Distributed Activation Energy Model [11].
These kinetic models can be generally classified into model-fitting
methods, for which an assumption about the reaction mechanism is
needed, and model-free methods, requiring no assumptions [23].
Among the model-free methods, simplified DAEM has been proved to
derive accurate values of the kinetic parameters from non-isothermal
TGA pyrolysis tests for a broad variety of biomass types, e.g., lig­
nocellulosic biomass [24], microalgae [22], or even sewage sludge
[21]. In contrast, a consecutive-reaction model has been applied to
describe isothermal kinetics of biomass conversion by Bach et al. [25]
and Bates and Ghoniem [26].
There is a wide variety of designs for pyrolysis reactors available in
the literature, for instance fixed or fluidized beds, conical spouted beds,
rotating cones, ablative reactors, rotary kiln reactors, auger reactors,
drop tubes, microwave reactors, vacuum reactors, plasma reactors, and
Curie-point reactors [27]. Among them, bubbling fluidized bed reactors
2
Algal Research 51 (2020) 102031
Abbreviations
C1 Pseudo-component 1
C2 Pseudo-component 2
C3 Pseudo-component 3
CP Chlorella pyrenoidosa
DAEM Distributed Activation Energy Model
DTG Differential Thermogravimetric
FB Fresh Biomass
M Moisture
RB Reacting Biomass
RMSE Root Mean Square Error
SP Spirulina platensis
SR Solid Residue
TG Thermogravimetric
TGA Thermogravimetric Analysis
provide a high thermal inertia, fast heating rates for the biomass par­
ticles and high heat transfer coefficients, allowing the occurrence of
biomass pyrolysis under isothermal conditions [28]. These character­
istics of fluidized beds are optimal for maximizing the bio-oil obtained
from a fast pyrolysis process of biomass, consisting in a fast heating of
the feedstock, limiting the residence time of the pyrolysis vapors re­
leased and quickly condensing the condensable fraction of the pyrolysis
vapors [29]. However, industrial scaling of bubbling fluidized beds may
lead to reductions of the pyrolysis conversion efficiency due to ag­
glomeration problems [30] and/or limited lateral mixing [31].
This work analyzes both the non-isothermal and isothermal pyr­
olysis processes of two different types of microalgae: Chlorella pyr­
enoidosa and Spirulina platensis. The non-isothermal pyrolysis is carried
out in a thermogravimetric analyzer, from which the commonly used
TG and DTG curves are obtained. These non-isothermal pyrolysis
measurements are employed to derive the pre-exponential factor and
the activation energy of the reaction through the use of the simplified
DAEM. As a novelty, the isothermal pyrolysis process of the microalgae
is conducted in a macro-TGA bubbling fluidized bed reactor. A con­
secutive reaction model, similar to that presented by Bach et al. [25]
and Bates and Ghoniem [26], is used for the characterization of the
kinetics of the microalgae in these isothermal conditions. However, this
isothermal model was modified to account for three different compo­
nents pyrolyzing separately. The experimental measurements of the
isothermal pyrolysis carried out in the fluidized bed reactor are used to
determine the pre-exponential factor and the activation energy of each
of the chemical reactions in the consecutive reaction model. Compar­
ison of the TGA non-isothermal pyrolysis and this novel isothermal
pyrolysis process will not only shed light on the particularities of the
pyrolysis of microalgae, but also provide new valuable information on
the relation of the non-isothermal and isothermal reaction kinetic
parameters and their implications in the modeling of pyrolysis pro­
cesses.
2. Theory
2.1. Non-isothermal pyrolysis
Non-isothermal pyrolysis measurements are typically conducted
under the controlled atmosphere of a thermogravimetric analyzer to
derive accurate values for the pyrolysis kinetic parameters, i.e., the pre-
exponential factor, A, and the activation energy, E. In the furnace of the
TGA, the solid samples are subjected to a specific temperature profile
under an inert atmosphere. Therefore, in the TGA, the temperature
increases at a constant heating rate β, from a low temperature around
100 °C to a high temperature above 700 °C. In consequence, for biomass
samples pyrolyzing in a temperature range from 300 to 600 °C, the
pyrolysis process occurring in a TGA is performed at non-isothermal
E. Cano-Pleite, et al.
conditions.
The simplified Distributed Activation Energy Model is a kinetic
method widely employed to describe non-isothermal pyrolysis of solid
fuels. The simplified DAEM assumes that the solid fuel is a complex
mixture of components whose thermal decomposition occurs as a
consequence of a large number of independent consecutive or si­
multaneous reactions. Each reaction is considered irreversible, of first
order, and is characterized by its corresponding activation energy and
pre-exponential factor. Under these assumptions, the pyrolysis con­
version of the solid fuel, α, using the simplified DAEM can be calculated
as follows:
( )
t
1 = exp A e E / RT dt f (E )dE ,
0 0
where α is the pyrolysis conversion at time t, R is the universal gas
constant, T is the temperature, f(E) is the probability density function of
the activation energy, and A and E are the pyrolysis kinetic parameters:
the pre-exponential factor and the activation energy, respectively. The
exponential term in the right-hand-size of Eq. (1) is denominated ϕ
function, which, considering a constant heating rate β, can be simplified
to an exponential function using the approximation of Murray and
White [32]:
A T ART 2
= exp e E / RT dT exp e E / RT
0 E
The expression obtained for the ϕ function in Eq. (2) can be further
simplified to a step function with a value of 0 for activation energies
below a specific value, E < Ea, and 1 for values above the activation
energy Ea. Miura [33] proved that a value of ϕ(Ea) = 0.58 is valid for a
broad variety of solid fuel samples. Using this step function simplifi­
cation for ϕ, together with the normalization criterion for the prob­
ability density function of the activation energy and a value of ϕ = 0.58
in Eq. (2), the characteristic equation of the simplified DAEM is ob­
tained:
AR E1
ln = ln + 0.6075 .
T2 E RT
In view of the structure of Eq. (3), Miura and Maki [34] proposed a
procedure to derive the kinetic parameters of pyrolysis, A and E, from a
series of non-isothermal pyrolysis tests conducted in a TGA for different
heating rates, β. Following this procedure, the characteristic pre-ex­
ponential factor, A, and the activation energy, E, of the pyrolysis of the
samples can be determined for specific values of the pyrolysis conver­
sion, α.
The simplified DAEM has proven to be of great utility for the eva­
luation of the pyrolysis kinetic parameters of a solid fuel as a function of
the pyrolysis conversion. However, one of the limitations of this kinetic
model is its range of applicability, which is restricted to the use of
constant heating rates, i.e., linear temperature increases. Hence, the
mathematical procedure followed to derive the characteristic equation
of simplified DAEM, Eq. (3), was modified in previous works to obtain
characteristic equations valid for parabolic and positive exponential
temperature increases [35] and inverse exponential temperature in­
creases [36], extending the applicability of this pyrolysis kinetic model.
2.2. Modeling isothermal pyrolysis
In contrast to the non-isothermal conditions of a TGA, some com­
monly used reactors for pyrolysis processes, such as fluidized beds,
operate at isothermal conditions. In fluidized bed reactors, the high
thermal inertia of the bed material guarantees a homogeneous tem­
perature distribution within the bed. The solid fuel particles fed into a
fluidized bed are subjected to a fast heating process, much rapid than in
a TGA, in which the particles reach the temperature of the bed in few
seconds. Additionally, the fluidized bed maintains a constant and
Algal Research 51 (2020) 102031
Fig. 1. Sketch of the proposed biomass isothermal pyrolysis model (FB: fresh
biomass; M: moisture; RB: reacting biomass; SR: solid residue; C1, C2, C3:
pseudo-components).
(1) homogeneous temperature during the pyrolysis process, which ensures
a constant temperature of the reacting particles as they move inside the
bed. For these reasons, it can be considered that, in this kind of reactors,
the pyrolysis process occurs under isothermal conditions.
The present work proposes the use of a consecutive reaction model
consisting of three solid components, moisture, and pyrolysis vapors to
describe the isothermal pyrolysis of biomass. This model is similar to
the one originally proposed by Di Blasi and Lazetta [37] and later va­
lidated by Bates and Ghoniem [38,39] for biomass torrefaction. How­
ever, the model was modified here to describe the isothermal pyrolysis
of biomass by using a competitive first order mechanism with three
. pseudo-components for the released pyrolysis vapors, instead of only
(2)
one gaseous compound, as proposed originally by Di Blasi and Lazetta
[37]. A sketch of the mechanism proposed for isothermal pyrolysis of
biomass is shown in Fig. 1. The fresh biomass FB releases moisture M
and converts into reacting biomass RB. This reacting biomass releases
the pyrolysis vapors based on the reaction of three competitive pseudo-
components C1, C2 and C3, and produces a solid residue SR, which
remains in the reactor after the pyrolysis is completed. This model
could be applied to the pyrolysis of lignocellulosic biomass, for which
the three pseudo-components C1, C2 and C3 would correspond to
hemicellulose, cellulose and lignin [40], and also to the pyrolysis of
microalgae, for which these three pseudo-components would be car­
bohydrates, proteins and lipids [11].
(3) The rate coefficient of each reaction in Fig. 1, ki, can be expressed as
a function of temperature T using Arrhenius' equation, based on the pre-
exponential factor and the activation energy of each reaction, Ai and Ei,
respectively:
Ei
ki = Ai exp i = FB, RB, SR, M, C1, C2, C3.
RT (4)
Considering the reaction mechanism shown in Fig. 1, the rate of
variation of the percentage of mass of each component, dXi/dt, can be
determined as a function of the rate coefficient of each reaction, ki, and
the remaining percentage of mass of each component, Xi, as follows:
dXFB
= (kRB + kM ) XFB ,
dt (5)
dXRB
= kRB XFB (kSR + kC1 + kC 2 + kC3 ) XRB ,
dt (6)
dXSR
= kSR XRB ,
dt (7)
dXCj
= kCj XRB j = 1, 2, 3.
dt (8)
The system of differential equations Eqs. (5)–(8) constitutes an ei­
genvalues problem, which can be solved to obtain the time evolution of
the remaining percentage of mass of each compound, Xi. The initial
conditions of the problem consider that the initial component is only
fresh biomass, thus, for t = 0 s → XFB = 100%, whereas the initial
percentage of all the rest of compounds is null, i.e.,
XRB = XSR = XM = XC1 = XC2 = XC3 = 0%.
Once the remaining percentage of mass of each compound, Xi, is
3
E. Cano-Pleite, et al.
expressed as a function of time, t, the time evolution of the remaining
percentage of mass (with regard to the initial mass of the samples) in
the reactor, X, can be obtained considering the release of all the gaseous
components: moisture and the pseudo-components C1, C2 and C3.
X = 100 (XM + XC1 + XC 2 + XC3 ). (9)
Therefore, the expression of Eq. (9) can be fitted to the measure­
ment of the time evolution of the remaining percentage of mass in the
reactor, X, obtained during isothermal pyrolysis processes. This fitting
is done via a non-linear least squares optimization process, which al­
lows to obtain the kinetic parameters of each reaction, Ai and Ei, as
fitting parameters of the consecutive reaction model with the experi­
mental results.
3. Materials and methods
3.1. Characterization of microalgae
Food grade Chlorella pyrenoidosa and Spirulina platensis were pur­
chased from Be Natur Plus Limitless Pharma (Spain) in tablets of 1 cm
in diameter. The thickness of the tablets is 0.5 cm for C. pyrenoidosa and
0.6 cm for S. platensis. In both cases, the purity of the microalgae in the
tablets is 100%. The tablets were crushed, and the samples were pul­
verized prior the basic characterization of the microalgae and the non-
isothermal pyrolysis tests in the TGA. In contrast, the isothermal pyr­
olysis experiments in the fluidized bed were conducted directly sup­
plying a specific number of tablets for each microalga from the top part
of the reactor.
A basic characterization of the microalgae used as feedstock was
conducted. The characterization consists in a proximate analysis and an
ultimate analysis, performed in a thermogravimetric analyzer TGA
Q500 (TA Instruments, Delaware, USA) and in an elemental analyzer
Leco TruSpec CHN and TruSpec S (LECO Corporation, Michigan, USA),
respectively. A detailed description of the basic characterization tests,
together with the accuracy of the equipment employed, can be found in
de Palma et al. [41]. The results of the basic characterization of the
microalgae samples of C. pyrenoidosa and S. platensis, obtained as the
average of three measurements, are reported in Table 1.
The volatile matter and ash content of both microalgae are similar,
obtaining values around 75%db and 10%db, respectively, for both C.
pyrenoidosa and S. platensis. The elemental composition of C. pyr­
enoidosa and S. platensis, obtained from the ultimate analysis, is also
similar for both species. In both cases, the content of carbon is much
higher than the content on the rest of elements. The nitrogen content,
compared to other biomass types, is high. The content of carbon of C.
pyrenoidosa is slightly higher than that of S. platensis, whereas S. pla­
tensis is characterized by a higher content on nitrogen. Regarding the
contents on hydrogen and sulfur, the results of the elemental analysis
for C. pyrenoidosa and S. platensis are close to 7%daf for hydrogen and
1%daf for sulfur in both cases. The results of the basic characterization
of C. pyrenoidosa are in good agreement with those reported in the
literature [13,18,42,43], whereas the results obtained for S. platensis
also match with those previously reported by [13,44,45].
3.2. Pyrolysis measurements in thermogravimetric analyzer
For the pyrolysis measurements in TGA, a mass of 5.0 ± 0.5 mg of
pulverized C. pyrenoidosa or S. platensis was loaded in a platinum pan.
Preliminary C. pyrenoidosa pyrolysis tests, using variable initial masses,
demonstrated that negligible heat and mass transfer effects occurred for
this initial mass. A flow rate of 60 ml/min of nitrogen was supplied to
the TGA furnace to guarantee inert conditions during pyrolysis. The
preparation of the samples and the temperature profile during the
pyrolysis tests were the same as those used in Soria-Verdugo et al. [46].
First, the samples were subjected to a temperature increase from room
temperature to 105 °C at a heating rate of 20 °C/min. Then, an
4
Algal Research 51 (2020) 102031
isothermal process of 30 min at 105 °C was programmed to completely
dry the samples prior to pyrolysis. Finally, the temperature was further
increased at a constant heating rate β from 105 to 700 °C. Note that the
conversion of microalgae during pyrolysis is usually operated in a
temperature range from 400 to 600 °C [47], confirming the appro­
priateness of the prescribed temperature range. To derive accurate
values of the kinetic parameters of the microalgae pyrolysis, nine dif­
ferent heating rates β = 10, 13, 16, 19, 22, 25, 30, 35 and 40 °C/min
were used, as recommended by Soria-Verdugo et al. [48]. For all cases,
the pyrolysis of C. pyrenoidosa and S. platensis in the TGA occurred
under non-isothermal conditions in a temperature range from 150 to
600 °C, in agreement with the maximum value of the temperature range
in Chen et al. [47]. The thermogravimetric tests for each microalga and
heating rate were replicated three times to ensure the repetitiveness of
the process.
3.3. Pyrolysis measurements in fluidized bed
The pyrolysis measurements in the fluidized bed were performed in
a lab-scale reactor of 4.7 cm in diameter and a total height of 50 cm.
The lateral walls of the reactor and the plenum were surrounded by
three electric resistors of 400 W to supply the thermal power required
to reach the desired bed temperature. The thermal power delivered by
the electric resistors was controlled by a potentiometer. A mass of 257 g
of fresh silica sand was used as bed material for each test. This material
was chosen due to its inert behavior during biomass thermochemical
conversion [49,50]. Nitrogen was used in the reactor as fluidizing agent
to prevent the presence of oxygen in the bed during the pyrolysis tests.
The nitrogen flow rate was supplied from a B50 bottle (Linde AG,
Munich, Germany), containing nitrogen 5.0 at a pressure of 200 bar.
The nitrogen flow rate was controlled by a flow regulator and measured
by a digital flowmeter PFM710-C6-E (SMC Corporation, Tokyo, Japan),
with a measurement range from 0.2 to 10 l/min. The fluidized bed
reactor was installed on a scale PS 6000 R2 (RADWAG Balances and
Scales, Toruńska, Poland) with a maximum range of 6 kg and a re­
solution of 0.01 g. The resolution of the scale is high enough to accu­
rately measure the evolution of the mass of the samples during the
pyrolysis process. The scale can measure the time evolution of the mass
of a biomass sample, supplied as a batch of 10.0 ± 0.5 g, in a similar
way to a thermogravimetric analyzer. In fact, the system formed by the
fluidized bed reactor laterally covered by the electric resistors and in­
stalled on the scale can be considered to constitute a macro-TGA. Fur­
ther increasing the resolution of the scale would not provide additional
valuable information of the mass evolution of the microalgae samples
during the pyrolysis process. More details about the experimental setup,
together with a schematic of the facility, can be found in previous works
[51,52].
The experimental procedure for the isothermal pyrolysis experi­
ments in the lab-scale fluidized bed consists in fluidizing the bed with
nitrogen at a velocity of 2.5 times the minimum fluidization velocity of
the bed material to ensure a bubbling fluidized bed regime of the bed
[28]. The minimum fluidization velocity was determined for each bed
temperature using the Carman-Kozeny correlation, following the
Table 1
Results of the basic characterization of Chlorella pyrenoidosa (CP) and Spirulina
platensis (SP) microalgae (M: Moisture, VM: Volatile Matter, A: Ash, C: Carbon,
H: Hydrogen, N: Nitrogen, S: Sulfur, O: Oxygen, db: dry basis, daf: dried ash free
basis, *calculated by difference). Values from three tests, attaining deviations
below ± 1.5%.
Proximate analysis [%db] Ultimate analysis [%daf]
VM A C H N S O*
CP 77.1 10.5 56.6 7.3 11.2 0.8 24.1
SP 75.7 9.9 53.9 7.4 12.5 1.1 25.1
E. Cano-Pleite, et al.
procedure described by Sánchez-Prieto et al. [53]. Heat was supplied by
the electric resistors through the vessel walls. The reactor temperature
was monitored by a type-K thermocouple immersed in the bed until the
desired bed temperature was reached. Once the bed temperature was
attained, the thermocouple was removed to prevent it from perturbing
the scale measurements and the bed dynamics, the gas velocity was
adjusted, the scale was tared and the microalgae tablets were supplied
through the top of the bed. The mass of the batch sample was attained
using 25 tablets of C. pyrenoidosa and 20 tablets of S. platensis, due to
the difference in size of the particles. Then, the time evolution of the
mass of the batch sample was monitored by the scale, while pyrolysis of
the freely moving C. pyrenoidosa and S. platensis particles occurred in
the bed. The isothermal pyrolysis tests in the fluidized bed were con­
ducted for each microalga for bed temperatures of 450, 500 and 550 °C,
corresponding to the optimal temperature range to maximize the gen­
eration of bio-oil from the condensation of pyrolysis vapors [29] and
within the conversion temperature range of microalgae during pyrolysis
[47]. An independent pyrolysis test operating the bed at 500 °C with a
gas velocity of 2.5Umf, using 25 tables of C. pyrenoidosa as a fuel, proved
that the decrease of bed temperature caused by the endothermic pyr­
olysis reactions was around 10 °C. Therefore, the pyrolysis of the mi­
croalgae inside the fluidized bed is considered to have a marginal effect
on the reactor temperature. Each test was replicated twice to guarantee
the repetitiveness of the experimental procedure. This facility and ex­
perimental setup were already used to study the pyrolysis of sewage
sludge [51] and Cynara cardunculus L. [52], and to analyze the sub­
limation of dry ice [54].
Fig. 2. Thermogravimetric (top) and differential thermogravimetric (bottom) curves for Chlorella pyrenoidosa (CP) and Spirulina platensis (SP) non-isothermal pyr­
olysis in a thermogravimetric analyzer. Data from three tests, obtaining deviations below ± 1%.
5
Algal Research 51 (2020) 102031
4. Results and discussion
4.1. Non-isothermal pyrolysis
The evolution of the pyrolysis conversion α with temperature T can
be obtained as a function of the evolution of mass of the sample and the
mass of the solid residue generated after pyrolysis from the non-iso­
thermal pyrolysis tests run in the TGA. The TG curves of C. pyrenoidosa
and S. platensis, representing the pyrolysis conversion α as a function of
temperature T, are depicted in Fig. 2. In both cases, a sharp increase of
the pyrolysis conversion occurs for temperatures above 250 °C. The
conversion during C. pyrenoidosa and S. platensis pyrolysis takes place
principally in a temperature range from 250 to 450 °C. Increasing the
heating rate, β, displaces the pyrolysis conversion of both microalgae to
higher temperatures, a common result reported in the literature for
non-isothermal pyrolysis processes [55,56].
The effect of the heating rate on the non-isothermal pyrolysis pro­
cess can be better observed in the DTG curves, which represent the rate
of pyrolysis conversion dα/dt as a function of temperature. The DTG
curves of C. pyrenoidosa and S. platensis non-isothermal pyrolysis in the
TGA are also included in Fig. 2. These DTG curves show an increase of
the conversion rate with the heating rate, also obtaining the maximum
conversion rate at higher temperatures, as stated in the Kissinger
method [57]. Two overlapping main peaks and a third underlying peak
distributed in a wider temperature range can be observed in the DTG
curve of C. pyrenoidosa, whereas a singular main sharp peak appears in
the S. platensis DTG curve, also together with an underlying peak dis­
tributed in a wider temperature range. The appearance of a singular
main peak during the non-isothermal pyrolysis of S. platensis is
E. Cano-Pleite, et al.
attributed to the higher content of proteins of this microalga compared
to its content in carbohydrates and lipids [47,58]. Microalgae mainly
consists of carbohydrates, proteins and lipids that degrade at different
temperature ranges, with a minor reaction peak at 241–261 °C and
major reaction peak at 316–353 °C for carbohydrates, 285–301 °C for
proteins and around 400 °C for lipids [59]. The decomposition of lipids
is not easily discernible in Fig. 2 due to the low content of lipids of both
microalgae: below 9% for S. platensis and below 2% for C. pyrenoidosa
[13,18,58,60]. However, it can be attributed to the underlying peak
present, for both microalgae, at a temperature of around 400 °C in their
corresponding DTG curves, in good agreement with Bach and Chen
[59]. In Fig. 2, a single peak appears in the DTG curve of S. platensis
while two observable peaks are depicted in the DTG curve of C. pyr­
enoidosa. This can be attributed to the different composition in carbo­
hydrates and proteins of the microalgae. Specifically, S. platensis pre­
sents a lower content of carbohydrates (8–19%) as compared to C.
pyrenoidosa (~24%) [13,18,58,60], which may be the main cause of the
different shape of their DTG curves. Furthermore, S. platensis is char­
acterized by faster pyrolysis conversion rates, which can be observed by
higher values of dα/dt in the DTG curve and by a sharper increase of the
conversion α in the TG curve.
Following the procedure proposed by Miura and Maki [34], the
temperature T at which specific values of the pyrolysis conversion, α,
are attained for each heating rate, β, can be obtained from the TG
curves. The range of pyrolysis conversion considered was from 10 to
90%, in intervals of 1%. The Arrhenius plot of C. pyrenoidosa and S.
platensis, depicting ln(β/T2) versus 1/T, is shown in Fig. 3, using in­
tervals of the pyrolysis conversion of 5% to improve the visualization of
the figure. The Arrhenius plot of each microalga shows a high linearity
of the data obtained for different heating rates, β, for specific values of
α. In fact, the average determination coefficient of a linear fitting of the
data shown in the Arrhenius plots is 0.994 for C. pyrenoidosa and 0.990
for S. platensis. These high values of the fitting coefficient prove the
reliability of the process and the accuracy of the non-isothermal pyr­
olysis measurements conducted in the TGA [61].
The linearization of the data included in the Arrhenius plots for
specific values of the pyrolysis conversion allows the derivation of the
kinetic parameters of the pyrolysis reaction, i.e., pre-exponential factor
A and activation energy E, as a function of the conversion, α. In view of
Eq. (3), the activation energy E can be determined from the slope of the
linear fitting, whereas the pre-exponential factor, A, is calculated from
the y-intercept in Fig. 3. The evolution of the kinetic parameters of C.
pyrenoidosa and S. platensis pyrolysis with the conversion is shown in
Fig. 4. The evolution of the activation energy and the pre-exponential
factors can be divided in two stages: a first stage in which the activation
energy remains generally uniform, while the pre-exponential factor
Fig. 3. Arrhenius plots for Chlorella pyrenoidosa (CP) and Spirulina platensis (SP) non-isothermal pyrolysis in a thermogravimetric analyzer for a conversion range from
10 to 90% in intervals of 5%.
6
Algal Research 51 (2020) 102031
decreases for values of the conversion below 70% and a second stage in
which both the activation energy and the pre-exponential factor rapidly
increase with the conversion. These stages can be associated to the
active and passive pyrolysis phases. Active pyrolysis occurs at medium
temperatures and corresponds to the reaction of the proteins and car­
bohydrates of the microalgae. The passive zone takes place at higher
temperatures and is considered to be dominated by the pyrolysis of the
lipids contained in the microalgae and the slower pyrolysis of the
generated solid residue. The increasing values of both the activation
energy and pre-exponential factors at the final stages of the pyrolysis
conversion are a result of the increasing importance of the passive stage
of pyrolysis. Overall, the activation energy of C. pyrenoidosa is within
the range of 150 and 275 kJ/mol, while its pre-exponential factor varies
from 1012 to 1019 s−1. These kinetic parameters for C. pyrenoidosa
pyrolysis are similar to those reported in previous works [21,42]. Re­
garding S. platensis, the activation energy is between 175 and 300 kJ/
mol, whereas the pre-exponential factor ranges from 1013 and 1020 s−1.
The kinetic parameters of S. platensis pyrolysis are also in good agree­
ment with those previously reported in the literature [24,44].
4.2. Isothermal pyrolysis
The isothermal pyrolysis tests were conducted in the lab-scale flui­
dized bed reactor supplying the microalgae tablets from the top part of
the bed. The time evolution of the mass of the whole reactor was
monitored by the scale during the pyrolysis process, with the reacting
particles freely circulating inside the bed. The scale was tared before
feeding the microalgae tablets to the bed, which allowed to directly
monitor the variation of mass of the samples during the experiment. As
an example, Fig. 5 shows the mass registered by the scale for the iso­
thermal pyrolysis of C. pyrenoidosa and S. platensis particles in a bub­
bling fluidized bed operated at a gas velocity of U = 2.5·Umf and a bed
temperature of Tb = 550 °C. In both cases, the batch of particles was
supplied through the top of the bed approximately 2 s after triggering
the data acquisition system, causing a fast increase of the mass regis­
tered by the scale to around 10 g. The mass measured by the scale
gradually decreases with time due to the release of the pyrolysis vapors
during the experiment. The remaining mass of the samples is stable
around values of 4 g after 150 s of experiment, illustrating the presence
of a solid residue after the pyrolysis process has been completed. Some
fluctuations can be observed in the mass measured for both microalgae
because of the bubbling regime imposed in the bed. The presence of
bubbles in the bed improves the dispersion of the microalgae particles
throughout the whole bed, however, the eruption of bubbles at the bed
surface ejects bed material to the freeboard, causing a variation of the
mass measured by the scale. Nevertheless, these fluctuations of the
E. Cano-Pleite, et al.
Fig. 4. Evolution of the pre-exponential factor, A, and activation energy, E, of the non-isothermal pyrolysis of Chlorella pyrenoidosa and Spirulina platensis in a
thermogravimetric analyzer as a function of the pyrolysis conversion, α.
mass registered by the scale are low enough to allow a clear evaluation
of the time evolution of the remaining mass of the samples in the re­
actor.
The time evolution of the percentage of mass remaining in the bed,
X, can be determined as the ratio of the sample mass remaining in the
reactor m and the initial mass of the sample m0. This time evolution is
depicted in Fig. 6 for the pyrolysis of C. pyrenoidosa and S. platensis at
bed temperatures of 450, 500, and 550 °C. In all cases, the initial point
of the test was considered when the mass registered by the scale is the
initial mass of the sample supplied. Fig. 6 shows that the kinetic model
used for the characterization of the isothermal pyrolysis is capable of
correctly predicting the evolution of the remaining mass of the batch
samples and, consequently, the mass of the remaining solid residue. A
similar effect of temperature on the isothermal pyrolysis of C. pyr­
enoidosa and S. platensis is observed in Fig. 6. In both cases, higher
temperatures result in a higher conversion of the sample due to the
larger amount of energy available in the bed [62,63]. However, the
effect of increasing the bed temperature of the pyrolysis is not the same
for both microalgae. The increase of the pyrolysis conversion of S.
platensis when increasing the bed temperature from 450 to 500 °C is
higher than that obtained for C. pyrenoidosa. In contrast, a higher in­
crease of conversion is observed for C. pyrenoidosa when increasing the
temperature from 500 to 550 °C compared to S. platensis.
The isothermal pyrolysis model presented in Section 2.2 was applied
to the experimental results obtained in the lab-scale fluidized bed. To
that end, the differential equation system, Eqs. (5)–(8), was analytically
Fig. 5. Evolution of the mass of the samples in the reactor for the isothermal pyrolysis of Chlorella pyrenoidosa (CP) and Spirulina platensis (SP) in a bubbling fluidized
bed operated at 2.5Umf and 550 °C.
7
Algal Research 51 (2020) 102031
solved to determine the percentage of mass of each component, Xi, as a
function of the kinetic parameters, i.e., Ai and Ei, of each reaction
shown in the sketch of the biomass isothermal pyrolysis model pro­
posed in Fig. 1. Then, an analytical expression was derived for the time
evolution of the percentage of mass remaining in the reactor X, using
Eq. (9). The time evolution of X obtained for each microalga was fitted
to the experimental measurements of the scale for the three bed tem­
peratures considered, obtaining the pre-exponential factors and the
activation energies of each pyrolysis reaction as fitting parameters. The
estimation of the remaining percentage of the mass of the samples
during pyrolysis of C. pyrenoidosa and S. platensis at 450, 500 and
550 °C, as provided by the pyrolysis model for the optimal kinetic
parameters, is also included in Fig. 6. The time evolution of the nu­
merical remaining percentage of mass was found to appropriately
follow the trend of the experimental measurements performed by the
scale for the pyrolysis of C. pyrenoidosa and S. platensis in a bubbling
fluidized bed at 450, 500 and 550 °C. In fact, the RMSE between the
experimental and the numerical time evolution of the remaining per­
centage of mass is below 3% for the pyrolysis of C. pyrenoidosa and
below 4% for S. platensis (see Table 2). These values of the RSME can be
considered low, especially in view of the variability of the experimental
measurements of the mass of the samples due to the eruption of bub­
bles, as shown in Fig. 6. The low values of the RMSE for all the bed
temperatures tested prove the validity of the isothermal model here
proposed to describe the pyrolysis process of microalgae in a bubbling
fluidized bed.
E. Cano-Pleite, et al. Algal Research 51 (2020) 102031

Fig. 6. Time evolution of the percentage of microalgae mass remaining in the bed for the isothermal pyrolysis of Chlorella pyrenoidosa (CP) and Spirulina platensis (SP)
in a bubbling fluidized bed operated at 2.5Umf.

Table 2 the pre-exponential factors of the reaction of the three pseudo-compo­

Deviation of the isothermal pyrolysis model and the experimental measure­ nents, ACi ~ 109–1013 s−1, are lower than those obtained from the TGA
ments of the percentage of mass remaining in the bed in terms of RMSE [%] measurements shown in Fig. 4, which can be explained by the existence
(CP: Chlorella pyrenoidosa, SP: Spirulina platensis). of consecutive reactions in the isothermal pyrolysis model, in contrast
Tb = 450 °C Tb = 500 °C Tb = 550 °C to the parallel reactions in the non-isothermal process. In view of the
results of Fig. 2 and Table 3, the number of required pseudo-compo­
CP 3.0 2.7 2.9 nents to model the pyrolysis process could be inferred from the number
SP 2.7 3.7 3.9
of peaks in the DTG curves of the microalgae, i.e., 3 for C. pyrenoidosa
and 2 for S. platensis. For S. platensis, the coincident values of the ac­
The pre-exponential factors and activation energies of each reaction tivation energies for the components C1 and C2 implies that the two
of the isothermal pyrolysis model of C. pyrenoidosa and S. platensis, reactions considered for the release of these two components can be
obtained as fitting parameters, are reported in Table 3. Similar values of simplified to a single reaction with the same activation energy, ob­
the kinetic parameters were obtained for the pyrolysis of the two mi­ taining exactly the same accuracy of the consecutive reaction model. In
croalgae. In both cases, the reaction of fresh biomass (FB) to produce contrast, the different values of the activation energy of each pseudo-
reacting biomass (RB) is characterized by very low values of A and E. component of C. pyrenoidosa, i.e., C1, C2 and C3, does not allow to
This implies that reacting biomass is produced fast once the fresh bio­ reduce the number of reactions of the consecutive reaction model
mass is supplied to the bed, as a result of the high bed temperature. The without reducing its accuracy to estimate the time evolution of the
kinetic parameters of the formation of moisture (M) and solid residue percentage of remaining mass during the isothermal pyrolysis of C.
(SR) are also similar for C. pyrenoidosa and S. platensis. In contrast, the pyrenoidosa in a bubbling fluidized bed.
kinetic parameters of the reaction of the reacting biomass to release the Once the isothermal pyrolysis model was validated with the ex­
three pseudo-components, i.e., C1, C2 and C3, differ. The values of the perimental measurements conducted in the lab-scale bubbling fluidized
activation energy of the three pseudo-components of C. pyrenoidosa are bed, the kinetic parameters of each reaction included in Table 3 can be
slightly different, revealing the existence of three main compounds that used to predict the time evolution of the remaining percentage of mass
are separately released during C. pyrenoidosa pyrolysis. However, the during the pyrolysis of C. pyrenoidosa and S. platensis for any tem­
activation energy of C1 and C2 are very similar for the pyrolysis of S. perature in the range from 450 to 550 °C. In that sense, the kinetic
platensis, differing from the value obtained for C3, indicating a si­ parameters shown in Table 3 were employed to determine the time
multaneous release of the former two pseudo-components. evolution of the remaining percentage of mass during the pyrolysis of C.
The different behavior observed for the C. pyrenoidosa and S. pla­ pyrenoidosa and S. platensis as predicted by the isothermal model for a
tensis isothermal pyrolysis, in terms of the kinetic parameters of the temperature range of 450–550 °C, using a temperature interval of 1 °C.
three pseudo-components released, is in good agreement with the re­ The percentage of mass produced as a solid residue of the microalgae
sults obtained from the non-isothermal pyrolysis tests run in the TGA,
revealing the usefulness of the non-isothermal kinetic parameters to Table 3
Kinetic parameters: pre-exponential factor, A, and activation energy, E, of the
provide a valid first approximation of the kinetic parameters in the
isothermal pyrolysis model obtained from the fitting of the time evolution of the
isothermal consecutive reaction model. The DTG curves of C. pyr­
percentage of microalgae mass remaining in the bed for each reaction (RB:
enoidosa depicted in Fig. 2 show two overlapping peaks whereas a reacting biomass; M: moisture; SR: solid residue; C1, C2, C3: pseudo-compo­
singular main peak was observed in the DTG curves of S. platensis, in nents).
addition to the underlying peak observed for both microalgae. The
Chlorella pyrenoidosa Spirulina platensis
values of the activation energy of the pseudo-components of C. pyr­
enoidosa in Table 3 are around 150, 160 and 230 kJ/mol, in accordance A [s −1
] E [kJ/mol] A [s−1] E [kJ/mol]
with the values derived from the non-isothermal kinetic analysis (see
−2 −6 −2
Fig. 4). The values of the activation energy for the isothermal pyrolysis RB 1.29·10 2.4·10 1.29·10 8.6·10−5
M 6.88·108 182.2 5.89·109 200.1
of C1, C2 and C3 of S. platensis are approximately 180, 180 and 240 kJ/
SR 3.73·109 154.4 2.70·1010 171.2
mol, respectively. These results are also in good agreement with the C1 1.16·109 151.8 9.41·1010 179.5
distribution of activation energy shown in Fig. 4 for the non-isothermal C2 7.53·109 159.8 9.41·1010 179.5
pyrolysis of S. platensis. In contrast, for both microalgae, the values of C3 9.32·1013 233.5 1.02·1011 243.3

8
E. Cano-Pleite, et al. Algal Research 51 (2020) 102031

pyrolysis at the end of the test, i.e., after 200 s, in the temperature range 5. Conclusions
from 450 to 550 °C was estimated by the model as a function of the bed
temperature. The percentage of solid residue generated was found to The non-isothermal and isothermal pyrolysis mechanisms of
follow a cubic relation with temperature for both C. pyrenoidosa and S. Spirulina platensis and Chlorella pyrenoidosa microalgae were in­
platensis, described by Eqs. (10) and (11), respectively, obtaining in vestigated in this work. The non-isothermal pyrolysis was carried out in
both cases determination coefficients of the cubic fitting above a TGA using different heating rates for temperatures up to 600 °C. The
R2 > 0.999. The percentage of solid residue XSR is obtained in % in­ simplified DAEM was applied to the results obtained from the TGA and
troducing the bed temperature Tb in °C in Eq. (10) for C. pyrenoidosa allowed to determine the pre-exponential factor and the activation
and Eq. (11) for S. platensis. energy of the two microalgae used in this work as a function of the
pyrolysis conversion. The DTG curves obtained in the TGA revealed the
XSR = 9.04·10 6Tb3 + 1.28·10 2Tb2 6.16Tb + 1041.40 (10) presence of a single main peak in the S. platensis DTG curve and two
main peaks in the C. pyrenoidosa DTG curve, also obtaining an under­
lying peak in both cases.
XSR = 1.46·10 5Tb3 + 2.2·10 2Tb2 11.12Tb + 1924.49 (11)
A first-order consecutive reaction model with three competitive
pseudo-components for the released pyrolysis vapors was proposed for
The cubic relations of Eqs. (10) and (11) of the percentage of solid
the analysis of the isothermal pyrolysis process. For the first time, a
residue produced during the isothermal pyrolysis of C. pyrenoidosa and
macro-TGA fluidized bed, capable of measuring the real-time mass
S. platensis with temperature are plotted in Fig. 7 together with the
evolution of the microalgae samples, was used to derive the kinetic
experimental results obtained from the measurement of the scale. These
parameters of the microalgae reactions, i.e., the pre-exponential factors
experimental values are represented in the figure as the average value
and activation energies of all the reactions in the model, through fitting
of the percentage of mass remaining during the last 10 s of the test, with
of experiments during an isothermal pyrolysis process. The model al­
an error bar corresponding to the standard deviation of the value for the
lows to obtain the kinetic parameters of the reactions, i.e., the pre-ex­
same time period. The cubic evolution of the solid residue generated
ponential factors and activation energies of all the reactions in the
with temperature predicted by the isothermal model is within the range
model, through fitting of experiments carried out in a macro-TGA
of variation of the experimental measurement for all cases. Further­
fluidized bed, which is capable of measuring the real-time mass evo­
more, the higher change on pyrolysis conversion attained for S. platensis
lution of the microalgae samples in the bed during an isothermal pyr­
compared to C. pyrenoidosa when increasing the temperature from 450
olysis process.
to 500 °C is also observed in Fig. 7. It should be recalled that the in­
The values of the activation energies obtained using the isothermal
terval 450–550 °C is chosen here because the production of bio-oil from
pyrolysis model are in very good agreement, both qualitatively and
the condensed vapors is maximum in this range [29].
quantitatively, with those obtained applying simplified DAEM to the
Despite the different nature of the common non-isothermal pyr­
TGA non-isothermal pyrolysis measurements. In particular, the values
olysis measurements conducted in TGA and the novel isothermal pyr­
of the activation energies obtained in the isothermal process present
olysis tests performed in a bubbling fluidized bed, the results here ob­
three different values for the C. pyrenoidosa pyrolysis and two different
tained from them are qualitatively comparable. The results revealed
values for the S. platensis conversion, which is similar to the number of
that the DTG curves obtained from the TGA measurements can be used
peaks observed in the DTG curves in the non-isothermal pyrolysis
to determine the number of reactions required to characterize the iso­
analysis. These findings are of paramount interest for isothermal and
thermal pyrolysis process by the number of peaks observed in the DTG
non-isothermal pyrolysis processes. Firstly, because they indicate that
curve. Furthermore, the kinetic parameters obtained from the non-
the non-isothermal TGA measurements could be used to provide a first
isothermal pyrolysis measurements in the controlled atmosphere of a
estimation of the activation energy of each of the pseudo-components
TGA have demonstrated to be useful for a first estimation of the acti­
considered for the isothermal pyrolysis process. Secondly, because the
vation energy of each of the pseudo-components considered in the
DTG curves obtained from the TGA have demonstrated to be useful to
isothermal pyrolysis. These two findings are of particular relevance, as
evaluate the number of reactions required to characterize the iso­
they have direct implications in the development of future models de­
thermal pyrolysis process by the number of peaks observed in the DTG
voted to evaluating isothermal pyrolysis processes in fluidized bed re­
curve. This specific conclusion is crucial for the future development of
actors.
microalgae pyrolysis models on a reactor-like scale.

Fig. 7. Evolution of the solid residue generated during Chlorella pyrenoidosa (CP) and Spirulina platensis (SP) pyrolysis with temperature. The points average the
remaining percentage of mass during the last 10 s of the test, the error bar corresponds to the standard deviation during this same time period.

9
E. Cano-Pleite, et al.
CRediT authorship contribution statement
The experimental measurements of the pyrolysis of the various
microalgae species were conducted in the Carlos III University of
Madrid (Spain). The non-isothermal pyrolysis measurements in TGA
were conducted by Dr. Eduardo Cano-Pleite and Prof. Dr. Néstor
García-Hernando. The isothermal pyrolysis measurements in the bub­
bling fluidized bed reactor were performed by Dr. Eduardo Cano-Pleite,
Dr. Mariano Rubio-Rubio and Prof. Dr. Antonio Soria-Verdugo. The
kinetic parameters of the non-isothermal pyrolysis measurements were
obtained by Dr. Eduardo Cano-Pleite and Prof. Dr. Antonio Soria-
Verdugo. The kinetic model and the fitting of the isothermal pyrolysis
measurements were developed by Dr. Eduardo Cano-Pleite and Dr.
Mariano Rubio-Rubio. Finally, all the authors contributed to the dis­
cussion of the results and to writing the paper.
Informed consent (human/animal rights)
No conflicts, informed consent, human or animal rights applicable.
Declaration of competing interest
The authors declare that there are no potential, financial or other
interests that could be perceived to influence the outcomes of this re­
search.
Acknowledgments
This work has been partially funded by Programa de Atracción de
Talento (Modalidad 2) de la Comunidad de Madrid (Spain), with
number 2019-T2/AMB-15938.
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