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 [4], and their capacity to grow in non-arable land and even in waste­
water [5]. Microalgae are composed of three main pseudo-components,
Bio-fuels production has been traditionally based on edible biomass namely proteins, carbohydrates and lipids. In short, proteins are mac­
and non-food energy crops, corresponding to the first and second romolecules made up of monomers in polymerized chains, carbohy­
generation of bio-fuels, respectively. A high conversion efficiency can drates are sugar monomers or polysaccharides such as glucose, cellulose
be attained for first-generation bio-fuels. However, the use of edible and starch, and lipids are long hydrocarbon chains attached with car­
biomass for energy purposes resulted in social and political controversy boxyl functional groups [6].
[1] since this can lead to shortage of food, especially in underdeveloped Several techniques have been used to obtain liquid bio-fuels from
and developing countries. Second-generation bio-fuels are character­ microalgae due to their potential superior properties compared to lig­
ized by a lower conversion efficiency. Thus, they are not economically nocellulosic and waste biomass. The most widely used conversion
profitable, and their industrial production requires a huge extension of techniques, operating with either dry or wet microalgae, are algal lipid
arable land, leading again to controversy due to the competition of extraction and upgrading (ALU) and hydrothermal liquefaction (HTL)
edible and non-food crops for arable land [2]. The problem derived [7,8]. In contrast, high-quality bio-fuels can be also obtained from
from the first- and second-generation of bio-fuels can be solved by the pyrolysis of dry microalgae [9]. Pyrolysis consists in the thermal de­
third-generation bio-fuels, which are based on aquatic crops, e.g., algae gradation of a solid fuel in absence of oxygen, obtaining a solid residue
and microalgae. The use of microalgae as feedstock for bio-fuel gen­ (biochar), liquid products (bio-oil), and gas products (permanent gas).
eration has various advantages, such as their fast-growing capability The amount and quality of each yield obtained from pyrolysis depends
[3], their higher photosynthesis efficiency compared to terrestrial crops 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. Algal Research 51 (2020) 102031

Nomenclature Abbreviations
C1 Pseudo-component 1
A pre-exponential factor [s−1] C2 Pseudo-component 2
α degree of conversion [%] C3 Pseudo-component 3
β heating rate [K min−1] CP Chlorella pyrenoidosa
E activation energy [kJ/mol] DAEM Distributed Activation Energy Model
k rate coefficient [s−1] DTG Differential Thermogravimetric
m mass of the sample remaining [g] FB Fresh Biomass
m0 initial mass of the sample [g] M Moisture
R universal gas constant [J mol−1 K−1] RB Reacting Biomass
t time [min] RMSE Root Mean Square Error
T temperature [°C, K] SP Spirulina platensis
Tb bed temperature [°C] SR Solid Residue
X percentage of remaining mass of the sample [%] TG Thermogravimetric
XSR percentage of solid residue generated [%] TGA Thermogravimetric Analysis

biomass heating rate, residence time of pyrolysis vapors, biomass par­ provide a high thermal inertia, fast heating rates for the biomass par­
ticle size, biomass feeding rate, and reaction time [10]. ticles and high heat transfer coefficients, allowing the occurrence of
The kinetics of microalgae pyrolysis based on Thermogravimetric biomass pyrolysis under isothermal conditions [28]. These character­
Analyzer (TGA) measurements was deeply reviewed by Bach and Chen istics of fluidized beds are optimal for maximizing the bio-oil obtained
[11]. In their work, they provided a state-of-the-art revision on the from a fast pyrolysis process of biomass, consisting in a fast heating of
pyrolysis kinetics of various microalgae, where different models, in­ the feedstock, limiting the residence time of the pyrolysis vapors re­
cluding single reaction and distributed activation energy models, are leased and quickly condensing the condensable fraction of the pyrolysis
analyzed and discussed. The pyrolysis of microalgae has been widely vapors [29]. However, industrial scaling of bubbling fluidized beds may
studied in the literature for many species using different modeling lead to reductions of the pyrolysis conversion efficiency due to ag­
strategies [12]. For instance, the Vyazovkin method was applied by Gai glomeration problems [30] and/or limited lateral mixing [31].
et al. [13] to analyze the pyrolysis of Chlorella pyrenoidosa and Spirulina This work analyzes both the non-isothermal and isothermal pyr­
platensis. The Kissinger method was used to study the pyrolysis of olysis processes of two different types of microalgae: Chlorella pyr­
Nannochloropsis oculata [14], periphytic microalgae [15] and the salt- enoidosa and Spirulina platensis. The non-isothermal pyrolysis is carried
water cord grass Spartina alterniflora [16]. A multiple-step model was out in a thermogravimetric analyzer, from which the commonly used
used for the analysis of Chlorella vulgaris, Scenedesmus almeriensis and TG and DTG curves are obtained. These non-isothermal pyrolysis
Nannochloropsis gaditana [17]. The simplified Distributed Activation measurements are employed to derive the pre-exponential factor and
Energy Model (DAEM) has been extensively employed in the research of the activation energy of the reaction through the use of the simplified
several microalgae species, such as Chlorella pyrenoidosa [18], Chlorella DAEM. As a novelty, the isothermal pyrolysis process of the microalgae
sorokiniana [19], Monoraphidium [19], Chlorella humicola [20], Chlorella is conducted in a macro-TGA bubbling fluidized bed reactor. A con­
vulgaris [21], Nannochloropsis oculata [22], and Tetraselmis sp. [22]. secutive reaction model, similar to that presented by Bach et al. [25]
Even though there exist many kinetic studies in the literature analyzing and Bates and Ghoniem [26], is used for the characterization of the
the pyrolysis process of microalgae based on TGA measurements, stu­ kinetics of the microalgae in these isothermal conditions. However, this
dies comparing TGA measurements with pyrolysis in other reactors, isothermal model was modified to account for three different compo­
such as fixed or fluidized beds, are scarce. nents pyrolyzing separately. The experimental measurements of the
The biomass conversion rate during pyrolysis depends on the re­ isothermal pyrolysis carried out in the fluidized bed reactor are used to
actor design, for which a deep understanding of the chemical kinetics of determine the pre-exponential factor and the activation energy of each
the process is required. In this sense, non-isothermal pyrolysis mea­ of the chemical reactions in the consecutive reaction model. Compar­
surements conducted in thermogravimetric analyzers have been widely ison of the TGA non-isothermal pyrolysis and this novel isothermal
used to derive the biomass kinetic parameters of the pyrolysis process. pyrolysis process will not only shed light on the particularities of the
Various kinetic models have been developed to describe the pyrolysis of pyrolysis of microalgae, but also provide new valuable information on
biomass, including the single reaction model, multiple parallel reac­ the relation of the non-isothermal and isothermal reaction kinetic
tions models, series reaction or consecutive reaction models, iso­ parameters and their implications in the modeling of pyrolysis pro­
conversional models or the Distributed Activation Energy Model [11]. cesses.
These kinetic models can be generally classified into model-fitting
methods, for which an assumption about the reaction mechanism is
2. Theory
needed, and model-free methods, requiring no assumptions [23].
Among the model-free methods, simplified DAEM has been proved to
2.1. Non-isothermal pyrolysis
derive accurate values of the kinetic parameters from non-isothermal
TGA pyrolysis tests for a broad variety of biomass types, e.g., lig­
Non-isothermal pyrolysis measurements are typically conducted
nocellulosic biomass [24], microalgae [22], or even sewage sludge
under the controlled atmosphere of a thermogravimetric analyzer to
[21]. In contrast, a consecutive-reaction model has been applied to
derive accurate values for the pyrolysis kinetic parameters, i.e., the pre-
describe isothermal kinetics of biomass conversion by Bach et al. [25]
exponential factor, A, and the activation energy, E. In the furnace of the
and Bates and Ghoniem [26].
TGA, the solid samples are subjected to a specific temperature profile
There is a wide variety of designs for pyrolysis reactors available in
under an inert atmosphere. Therefore, in the TGA, the temperature
the literature, for instance fixed or fluidized beds, conical spouted beds,
increases at a constant heating rate β, from a low temperature around
rotating cones, ablative reactors, rotary kiln reactors, auger reactors,
100 °C to a high temperature above 700 °C. In consequence, for biomass
drop tubes, microwave reactors, vacuum reactors, plasma reactors, and
samples pyrolyzing in a temperature range from 300 to 600 °C, the
Curie-point reactors [27]. Among them, bubbling fluidized bed reactors
pyrolysis process occurring in a TGA is performed at non-isothermal

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

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 Fig. 1. Sketch of the proposed biomass isothermal pyrolysis model (FB: fresh
version of the solid fuel, α, using the simplified DAEM can be calculated biomass; M: moisture; RB: reacting biomass; SR: solid residue; C1, C2, C3:
as follows: pseudo-components).

( )
t
1 = exp A e E / RT dt f (E )dE ,
0 0 (1) homogeneous temperature during the pyrolysis process, which ensures
a constant temperature of the reacting particles as they move inside the
where α is the pyrolysis conversion at time t, R is the universal gas
bed. For these reasons, it can be considered that, in this kind of reactors,
constant, T is the temperature, f(E) is the probability density function of
the pyrolysis process occurs under isothermal conditions.
the activation energy, and A and E are the pyrolysis kinetic parameters:
The present work proposes the use of a consecutive reaction model
the pre-exponential factor and the activation energy, respectively. The
consisting of three solid components, moisture, and pyrolysis vapors to
exponential term in the right-hand-size of Eq. (1) is denominated ϕ
describe the isothermal pyrolysis of biomass. This model is similar to
function, which, considering a constant heating rate β, can be simplified
the one originally proposed by Di Blasi and Lazetta [37] and later va­
to an exponential function using the approximation of Murray and
lidated by Bates and Ghoniem [38,39] for biomass torrefaction. How­
White [32]:
ever, the model was modified here to describe the isothermal pyrolysis
A T ART 2 of biomass by using a competitive first order mechanism with three
= exp e E / RT dT exp e E / RT . pseudo-components for the released pyrolysis vapors, instead of only
0 E (2)
one gaseous compound, as proposed originally by Di Blasi and Lazetta
The expression obtained for the ϕ function in Eq. (2) can be further [37]. A sketch of the mechanism proposed for isothermal pyrolysis of
simplified to a step function with a value of 0 for activation energies biomass is shown in Fig. 1. The fresh biomass FB releases moisture M
below a specific value, E < Ea, and 1 for values above the activation and converts into reacting biomass RB. This reacting biomass releases
energy Ea. Miura [33] proved that a value of ϕ(Ea) = 0.58 is valid for a the pyrolysis vapors based on the reaction of three competitive pseudo-
broad variety of solid fuel samples. Using this step function simplifi­ components C1, C2 and C3, and produces a solid residue SR, which
cation for ϕ, together with the normalization criterion for the prob­ remains in the reactor after the pyrolysis is completed. This model
ability density function of the activation energy and a value of ϕ = 0.58 could be applied to the pyrolysis of lignocellulosic biomass, for which
in Eq. (2), the characteristic equation of the simplified DAEM is ob­ the three pseudo-components C1, C2 and C3 would correspond to
tained: hemicellulose, cellulose and lignin [40], and also to the pyrolysis of
microalgae, for which these three pseudo-components would be car­
AR E1 bohydrates, proteins and lipids [11].
ln = ln + 0.6075 .
T2 E RT (3) The rate coefficient of each reaction in Fig. 1, ki, can be expressed as
In view of the structure of Eq. (3), Miura and Maki [34] proposed a a function of temperature T using Arrhenius' equation, based on the pre-
procedure to derive the kinetic parameters of pyrolysis, A and E, from a exponential factor and the activation energy of each reaction, Ai and Ei,
series of non-isothermal pyrolysis tests conducted in a TGA for different respectively:
heating rates, β. Following this procedure, the characteristic pre-ex­ Ei
ki = Ai exp i = FB, RB, SR, M, C1, C2, C3.
ponential factor, A, and the activation energy, E, of the pyrolysis of the RT (4)
samples can be determined for specific values of the pyrolysis conver­
Considering the reaction mechanism shown in Fig. 1, the rate of
sion, α.
variation of the percentage of mass of each component, dXi/dt, can be
The simplified DAEM has proven to be of great utility for the eva­
determined as a function of the rate coefficient of each reaction, ki, and
luation of the pyrolysis kinetic parameters of a solid fuel as a function of
the remaining percentage of mass of each component, Xi, as follows:
the pyrolysis conversion. However, one of the limitations of this kinetic
model is its range of applicability, which is restricted to the use of dXFB
= (kRB + kM ) XFB ,
constant heating rates, i.e., linear temperature increases. Hence, the dt (5)
mathematical procedure followed to derive the characteristic equation
dXRB
of simplified DAEM, Eq. (3), was modified in previous works to obtain = kRB XFB (kSR + kC1 + kC 2 + kC3 ) XRB ,
dt (6)
characteristic equations valid for parabolic and positive exponential
temperature increases [35] and inverse exponential temperature in­ dXSR
= kSR XRB ,
creases [36], extending the applicability of this pyrolysis kinetic model. dt (7)

dXCj
2.2. Modeling isothermal pyrolysis = kCj XRB j = 1, 2, 3.
dt (8)
In contrast to the non-isothermal conditions of a TGA, some com­ The system of differential equations Eqs. (5)–(8) constitutes an ei­
monly used reactors for pyrolysis processes, such as fluidized beds, genvalues problem, which can be solved to obtain the time evolution of
operate at isothermal conditions. In fluidized bed reactors, the high the remaining percentage of mass of each compound, Xi. The initial
thermal inertia of the bed material guarantees a homogeneous tem­ conditions of the problem consider that the initial component is only
perature distribution within the bed. The solid fuel particles fed into a fresh biomass, thus, for t = 0 s → XFB = 100%, whereas the initial
fluidized bed are subjected to a fast heating process, much rapid than in percentage of all the rest of compounds is null, i.e.,
a TGA, in which the particles reach the temperature of the bed in few XRB = XSR = XM = XC1 = XC2 = XC3 = 0%.
seconds. Additionally, the fluidized bed maintains a constant and Once the remaining percentage of mass of each compound, Xi, is

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

expressed as a function of time, t, the time evolution of the remaining isothermal process of 30 min at 105 °C was programmed to completely
percentage of mass (with regard to the initial mass of the samples) in dry the samples prior to pyrolysis. Finally, the temperature was further
the reactor, X, can be obtained considering the release of all the gaseous increased at a constant heating rate β from 105 to 700 °C. Note that the
components: moisture and the pseudo-components C1, C2 and C3. conversion of microalgae during pyrolysis is usually operated in a
temperature range from 400 to 600 °C [47], confirming the appro­
X = 100 (XM + XC1 + XC 2 + XC3 ). (9)
priateness of the prescribed temperature range. To derive accurate
Therefore, the expression of Eq. (9) can be fitted to the measure­ values of the kinetic parameters of the microalgae pyrolysis, nine dif­
ment of the time evolution of the remaining percentage of mass in the ferent heating rates β = 10, 13, 16, 19, 22, 25, 30, 35 and 40 °C/min
reactor, X, obtained during isothermal pyrolysis processes. This fitting were used, as recommended by Soria-Verdugo et al. [48]. For all cases,
is done via a non-linear least squares optimization process, which al­ the pyrolysis of C. pyrenoidosa and S. platensis in the TGA occurred
lows to obtain the kinetic parameters of each reaction, Ai and Ei, as under non-isothermal conditions in a temperature range from 150 to
fitting parameters of the consecutive reaction model with the experi­ 600 °C, in agreement with the maximum value of the temperature range
mental results. in Chen et al. [47]. The thermogravimetric tests for each microalga and
heating rate were replicated three times to ensure the repetitiveness of
3. Materials and methods the process.

3.1. Characterization of microalgae 3.3. Pyrolysis measurements in fluidized bed

Food grade Chlorella pyrenoidosa and Spirulina platensis were pur­ The pyrolysis measurements in the fluidized bed were performed in
chased from Be Natur Plus Limitless Pharma (Spain) in tablets of 1 cm a lab-scale reactor of 4.7 cm in diameter and a total height of 50 cm.
in diameter. The thickness of the tablets is 0.5 cm for C. pyrenoidosa and The lateral walls of the reactor and the plenum were surrounded by
0.6 cm for S. platensis. In both cases, the purity of the microalgae in the three electric resistors of 400 W to supply the thermal power required
tablets is 100%. The tablets were crushed, and the samples were pul­ to reach the desired bed temperature. The thermal power delivered by
verized prior the basic characterization of the microalgae and the non- the electric resistors was controlled by a potentiometer. A mass of 257 g
isothermal pyrolysis tests in the TGA. In contrast, the isothermal pyr­ of fresh silica sand was used as bed material for each test. This material
olysis experiments in the fluidized bed were conducted directly sup­ was chosen due to its inert behavior during biomass thermochemical
plying a specific number of tablets for each microalga from the top part conversion [49,50]. Nitrogen was used in the reactor as fluidizing agent
of the reactor. to prevent the presence of oxygen in the bed during the pyrolysis tests.
A basic characterization of the microalgae used as feedstock was The nitrogen flow rate was supplied from a B50 bottle (Linde AG,
conducted. The characterization consists in a proximate analysis and an Munich, Germany), containing nitrogen 5.0 at a pressure of 200 bar.
ultimate analysis, performed in a thermogravimetric analyzer TGA The nitrogen flow rate was controlled by a flow regulator and measured
Q500 (TA Instruments, Delaware, USA) and in an elemental analyzer by a digital flowmeter PFM710-C6-E (SMC Corporation, Tokyo, Japan),
Leco TruSpec CHN and TruSpec S (LECO Corporation, Michigan, USA), with a measurement range from 0.2 to 10 l/min. The fluidized bed
respectively. A detailed description of the basic characterization tests, reactor was installed on a scale PS 6000 R2 (RADWAG Balances and
together with the accuracy of the equipment employed, can be found in Scales, Toruńska, Poland) with a maximum range of 6 kg and a re­
de Palma et al. [41]. The results of the basic characterization of the solution of 0.01 g. The resolution of the scale is high enough to accu­
microalgae samples of C. pyrenoidosa and S. platensis, obtained as the rately measure the evolution of the mass of the samples during the
average of three measurements, are reported in Table 1. pyrolysis process. The scale can measure the time evolution of the mass
The volatile matter and ash content of both microalgae are similar, of a biomass sample, supplied as a batch of 10.0 ± 0.5 g, in a similar
obtaining values around 75%db and 10%db, respectively, for both C. way to a thermogravimetric analyzer. In fact, the system formed by the
pyrenoidosa and S. platensis. The elemental composition of C. pyr­ fluidized bed reactor laterally covered by the electric resistors and in­
enoidosa and S. platensis, obtained from the ultimate analysis, is also stalled on the scale can be considered to constitute a macro-TGA. Fur­
similar for both species. In both cases, the content of carbon is much ther increasing the resolution of the scale would not provide additional
higher than the content on the rest of elements. The nitrogen content, valuable information of the mass evolution of the microalgae samples
compared to other biomass types, is high. The content of carbon of C. during the pyrolysis process. More details about the experimental setup,
pyrenoidosa is slightly higher than that of S. platensis, whereas S. pla­ together with a schematic of the facility, can be found in previous works
tensis is characterized by a higher content on nitrogen. Regarding the [51,52].
contents on hydrogen and sulfur, the results of the elemental analysis The experimental procedure for the isothermal pyrolysis experi­
for C. pyrenoidosa and S. platensis are close to 7%daf for hydrogen and ments in the lab-scale fluidized bed consists in fluidizing the bed with
1%daf for sulfur in both cases. The results of the basic characterization nitrogen at a velocity of 2.5 times the minimum fluidization velocity of
of C. pyrenoidosa are in good agreement with those reported in the the bed material to ensure a bubbling fluidized bed regime of the bed
literature [13,18,42,43], whereas the results obtained for S. platensis [28]. The minimum fluidization velocity was determined for each bed
also match with those previously reported by [13,44,45]. temperature using the Carman-Kozeny correlation, following the

3.2. Pyrolysis measurements in thermogravimetric analyzer Table 1

Results of the basic characterization of Chlorella pyrenoidosa (CP) and Spirulina
For the pyrolysis measurements in TGA, a mass of 5.0 ± 0.5 mg of platensis (SP) microalgae (M: Moisture, VM: Volatile Matter, A: Ash, C: Carbon,
pulverized C. pyrenoidosa or S. platensis was loaded in a platinum pan. H: Hydrogen, N: Nitrogen, S: Sulfur, O: Oxygen, db: dry basis, daf: dried ash free
Preliminary C. pyrenoidosa pyrolysis tests, using variable initial masses, basis, *calculated by difference). Values from three tests, attaining deviations
demonstrated that negligible heat and mass transfer effects occurred for below ± 1.5%.
this initial mass. A flow rate of 60 ml/min of nitrogen was supplied to Proximate analysis [%db] Ultimate analysis [%daf]
the TGA furnace to guarantee inert conditions during pyrolysis. The
preparation of the samples and the temperature profile during the VM A C H N S O*
pyrolysis tests were the same as those used in Soria-Verdugo et al. [46].
CP 77.1 10.5 56.6 7.3 11.2 0.8 24.1
First, the samples were subjected to a temperature increase from room SP 75.7 9.9 53.9 7.4 12.5 1.1 25.1
temperature to 105 °C at a heating rate of 20 °C/min. Then, an

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

procedure described by Sánchez-Prieto et al. [53]. Heat was supplied by 4. Results and discussion
the electric resistors through the vessel walls. The reactor temperature
was monitored by a type-K thermocouple immersed in the bed until the 4.1. Non-isothermal pyrolysis
desired bed temperature was reached. Once the bed temperature was
attained, the thermocouple was removed to prevent it from perturbing The evolution of the pyrolysis conversion α with temperature T can
the scale measurements and the bed dynamics, the gas velocity was be obtained as a function of the evolution of mass of the sample and the
adjusted, the scale was tared and the microalgae tablets were supplied mass of the solid residue generated after pyrolysis from the non-iso­
through the top of the bed. The mass of the batch sample was attained thermal pyrolysis tests run in the TGA. The TG curves of C. pyrenoidosa
using 25 tablets of C. pyrenoidosa and 20 tablets of S. platensis, due to and S. platensis, representing the pyrolysis conversion α as a function of
the difference in size of the particles. Then, the time evolution of the temperature T, are depicted in Fig. 2. In both cases, a sharp increase of
mass of the batch sample was monitored by the scale, while pyrolysis of the pyrolysis conversion occurs for temperatures above 250 °C. The
the freely moving C. pyrenoidosa and S. platensis particles occurred in conversion during C. pyrenoidosa and S. platensis pyrolysis takes place
the bed. The isothermal pyrolysis tests in the fluidized bed were con­ principally in a temperature range from 250 to 450 °C. Increasing the
ducted for each microalga for bed temperatures of 450, 500 and 550 °C, heating rate, β, displaces the pyrolysis conversion of both microalgae to
corresponding to the optimal temperature range to maximize the gen­ higher temperatures, a common result reported in the literature for
eration of bio-oil from the condensation of pyrolysis vapors [29] and non-isothermal pyrolysis processes [55,56].
within the conversion temperature range of microalgae during pyrolysis The effect of the heating rate on the non-isothermal pyrolysis pro­
[47]. An independent pyrolysis test operating the bed at 500 °C with a cess can be better observed in the DTG curves, which represent the rate
gas velocity of 2.5Umf, using 25 tables of C. pyrenoidosa as a fuel, proved of pyrolysis conversion dα/dt as a function of temperature. The DTG
that the decrease of bed temperature caused by the endothermic pyr­ curves of C. pyrenoidosa and S. platensis non-isothermal pyrolysis in the
olysis reactions was around 10 °C. Therefore, the pyrolysis of the mi­ TGA are also included in Fig. 2. These DTG curves show an increase of
croalgae inside the fluidized bed is considered to have a marginal effect the conversion rate with the heating rate, also obtaining the maximum
on the reactor temperature. Each test was replicated twice to guarantee conversion rate at higher temperatures, as stated in the Kissinger
the repetitiveness of the experimental procedure. This facility and ex­ method [57]. Two overlapping main peaks and a third underlying peak
perimental setup were already used to study the pyrolysis of sewage distributed in a wider temperature range can be observed in the DTG
sludge [51] and Cynara cardunculus L. [52], and to analyze the sub­ curve of C. pyrenoidosa, whereas a singular main sharp peak appears in
limation of dry ice [54]. 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

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%.

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

attributed to the higher content of proteins of this microalga compared decreases for values of the conversion below 70% and a second stage in
to its content in carbohydrates and lipids [47,58]. Microalgae mainly which both the activation energy and the pre-exponential factor rapidly
consists of carbohydrates, proteins and lipids that degrade at different increase with the conversion. These stages can be associated to the
temperature ranges, with a minor reaction peak at 241–261 °C and active and passive pyrolysis phases. Active pyrolysis occurs at medium
major reaction peak at 316–353 °C for carbohydrates, 285–301 °C for temperatures and corresponds to the reaction of the proteins and car­
proteins and around 400 °C for lipids [59]. The decomposition of lipids bohydrates of the microalgae. The passive zone takes place at higher
is not easily discernible in Fig. 2 due to the low content of lipids of both temperatures and is considered to be dominated by the pyrolysis of the
microalgae: below 9% for S. platensis and below 2% for C. pyrenoidosa lipids contained in the microalgae and the slower pyrolysis of the
[13,18,58,60]. However, it can be attributed to the underlying peak generated solid residue. The increasing values of both the activation
present, for both microalgae, at a temperature of around 400 °C in their energy and pre-exponential factors at the final stages of the pyrolysis
corresponding DTG curves, in good agreement with Bach and Chen conversion are a result of the increasing importance of the passive stage
[59]. In Fig. 2, a single peak appears in the DTG curve of S. platensis of pyrolysis. Overall, the activation energy of C. pyrenoidosa is within
while two observable peaks are depicted in the DTG curve of C. pyr­ the range of 150 and 275 kJ/mol, while its pre-exponential factor varies
enoidosa. This can be attributed to the different composition in carbo­ from 1012 to 1019 s−1. These kinetic parameters for C. pyrenoidosa
hydrates and proteins of the microalgae. Specifically, S. platensis pre­ pyrolysis are similar to those reported in previous works [21,42]. Re­
sents a lower content of carbohydrates (8–19%) as compared to C. garding S. platensis, the activation energy is between 175 and 300 kJ/
pyrenoidosa (~24%) [13,18,58,60], which may be the main cause of the mol, whereas the pre-exponential factor ranges from 1013 and 1020 s−1.
different shape of their DTG curves. Furthermore, S. platensis is char­ The kinetic parameters of S. platensis pyrolysis are also in good agree­
acterized by faster pyrolysis conversion rates, which can be observed by ment with those previously reported in the literature [24,44].
higher values of dα/dt in the DTG curve and by a sharper increase of the
conversion α in the TG curve. 4.2. Isothermal pyrolysis
Following the procedure proposed by Miura and Maki [34], the
temperature T at which specific values of the pyrolysis conversion, α, The isothermal pyrolysis tests were conducted in the lab-scale flui­
are attained for each heating rate, β, can be obtained from the TG dized bed reactor supplying the microalgae tablets from the top part of
curves. The range of pyrolysis conversion considered was from 10 to the bed. The time evolution of the mass of the whole reactor was
90%, in intervals of 1%. The Arrhenius plot of C. pyrenoidosa and S. monitored by the scale during the pyrolysis process, with the reacting
platensis, depicting ln(β/T2) versus 1/T, is shown in Fig. 3, using in­ particles freely circulating inside the bed. The scale was tared before
tervals of the pyrolysis conversion of 5% to improve the visualization of feeding the microalgae tablets to the bed, which allowed to directly
the figure. The Arrhenius plot of each microalga shows a high linearity monitor the variation of mass of the samples during the experiment. As
of the data obtained for different heating rates, β, for specific values of an example, Fig. 5 shows the mass registered by the scale for the iso­
α. In fact, the average determination coefficient of a linear fitting of the thermal pyrolysis of C. pyrenoidosa and S. platensis particles in a bub­
data shown in the Arrhenius plots is 0.994 for C. pyrenoidosa and 0.990 bling fluidized bed operated at a gas velocity of U = 2.5·Umf and a bed
for S. platensis. These high values of the fitting coefficient prove the temperature of Tb = 550 °C. In both cases, the batch of particles was
reliability of the process and the accuracy of the non-isothermal pyr­ supplied through the top of the bed approximately 2 s after triggering
olysis measurements conducted in the TGA [61]. the data acquisition system, causing a fast increase of the mass regis­
The linearization of the data included in the Arrhenius plots for tered by the scale to around 10 g. The mass measured by the scale
specific values of the pyrolysis conversion allows the derivation of the gradually decreases with time due to the release of the pyrolysis vapors
kinetic parameters of the pyrolysis reaction, i.e., pre-exponential factor during the experiment. The remaining mass of the samples is stable
A and activation energy E, as a function of the conversion, α. In view of around values of 4 g after 150 s of experiment, illustrating the presence
Eq. (3), the activation energy E can be determined from the slope of the of a solid residue after the pyrolysis process has been completed. Some
linear fitting, whereas the pre-exponential factor, A, is calculated from fluctuations can be observed in the mass measured for both microalgae
the y-intercept in Fig. 3. The evolution of the kinetic parameters of C. because of the bubbling regime imposed in the bed. The presence of
pyrenoidosa and S. platensis pyrolysis with the conversion is shown in bubbles in the bed improves the dispersion of the microalgae particles
Fig. 4. The evolution of the activation energy and the pre-exponential throughout the whole bed, however, the eruption of bubbles at the bed
factors can be divided in two stages: a first stage in which the activation surface ejects bed material to the freeboard, causing a variation of the
energy remains generally uniform, while the pre-exponential factor mass measured by the scale. Nevertheless, these fluctuations of the

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%.

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

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 solved to determine the percentage of mass of each component, Xi, as a
of the time evolution of the remaining mass of the samples in the re­ function of the kinetic parameters, i.e., Ai and Ei, of each reaction
actor. shown in the sketch of the biomass isothermal pyrolysis model pro­
The time evolution of the percentage of mass remaining in the bed, posed in Fig. 1. Then, an analytical expression was derived for the time
X, can be determined as the ratio of the sample mass remaining in the evolution of the percentage of mass remaining in the reactor X, using
reactor m and the initial mass of the sample m0. This time evolution is Eq. (9). The time evolution of X obtained for each microalga was fitted
depicted in Fig. 6 for the pyrolysis of C. pyrenoidosa and S. platensis at to the experimental measurements of the scale for the three bed tem­
bed temperatures of 450, 500, and 550 °C. In all cases, the initial point peratures considered, obtaining the pre-exponential factors and the
of the test was considered when the mass registered by the scale is the activation energies of each pyrolysis reaction as fitting parameters. The
initial mass of the sample supplied. Fig. 6 shows that the kinetic model estimation of the remaining percentage of the mass of the samples
used for the characterization of the isothermal pyrolysis is capable of during pyrolysis of C. pyrenoidosa and S. platensis at 450, 500 and
correctly predicting the evolution of the remaining mass of the batch 550 °C, as provided by the pyrolysis model for the optimal kinetic
samples and, consequently, the mass of the remaining solid residue. A parameters, is also included in Fig. 6. The time evolution of the nu­
similar effect of temperature on the isothermal pyrolysis of C. pyr­ merical remaining percentage of mass was found to appropriately
enoidosa and S. platensis is observed in Fig. 6. In both cases, higher follow the trend of the experimental measurements performed by the
temperatures result in a higher conversion of the sample due to the scale for the pyrolysis of C. pyrenoidosa and S. platensis in a bubbling
larger amount of energy available in the bed [62,63]. However, the fluidized bed at 450, 500 and 550 °C. In fact, the RMSE between the
effect of increasing the bed temperature of the pyrolysis is not the same experimental and the numerical time evolution of the remaining per­
for both microalgae. The increase of the pyrolysis conversion of S. centage of mass is below 3% for the pyrolysis of C. pyrenoidosa and
platensis when increasing the bed temperature from 450 to 500 °C is below 4% for S. platensis (see Table 2). These values of the RSME can be
higher than that obtained for C. pyrenoidosa. In contrast, a higher in­ considered low, especially in view of the variability of the experimental
crease of conversion is observed for C. pyrenoidosa when increasing the measurements of the mass of the samples due to the eruption of bub­
temperature from 500 to 550 °C compared to S. platensis. bles, as shown in Fig. 6. The low values of the RMSE for all the bed
The isothermal pyrolysis model presented in Section 2.2 was applied temperatures tested prove the validity of the isothermal model here
to the experimental results obtained in the lab-scale fluidized bed. To proposed to describe the pyrolysis process of microalgae in a bubbling
that end, the differential equation system, Eqs. (5)–(8), was analytically fluidized bed.

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
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. Algal Research 51 (2020) 102031

CRediT authorship contribution statement Energy 9 (2015) 125–133.

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