Catalytic Pyrolysis of Spirulina platensis Residue (SPR): Thermochemical Behavior and Kinetics
Corresponding email: abudiman@ugm.ac.id
Published at : 21 Jul 2020
Volume : IJtech
Vol 11, No 3 (2020)
DOI : https://doi.org/10.14716/ijtech.v11i3.2967
Jamilatun, S., Budhijanto, Rochmadi, Yuliestyan, A., Aziz, M., Hayashi, J., Budiman, A., 2020. Catalytic Pyrolysis of Spirulina platensis Residue (SPR): Thermochemical Behavior and Kinetics. International Journal of Technology. Volume 11(3), pp. 522-531
| Siti Jamilatun | Department of Chemical Engineering, Faculty of Industrial Technology, Universitas Ahmad Dahlan, Jalan Kapas 9, Yogyakarta 55166, Indonesia |
| Budhijanto | Department of Chemical Engineering, Faculty of Engineering, Universitas Gadjah Mada, Jalan Grafika 2, Yogyakarta 55284, Indonesia |
| Rochmadi | Department of Chemical Engineering, Faculty of Engineering, Universitas Gadjah Mada, Jalan Grafika 2, Yogyakarta 55284, Indonesia |
| Avido Yuliestyan | Department of Chemical Engineering, Faculty of Industrial Technology, Universitas Pembangunan Nasional “Veteran” Yogyakarta, Jalan SWK 104, Yogyakarta 55283, Indonesia |
| Muhammad Aziz | -Institute of Innovative Research, Tokyo Institute of Technology, i6-25, 2-12-1 Ookayama, Meguro-ku, Tokyo 152-8550 Japan -Institute of Industrial Science, The University of Tokyo, 4-6-1 Komaba, Megu |
| Jun-ichiro Hayashi | Institute for Material Chemistry and Engineering, Kyushu University, Kasuga 816-8580 Japan |
| Arief Budiman | Department of Chemical Engineering, Faculty of Engineering, Universitas Gadjah Mada, Jalan Grafika 2, Yogyakarta 55284, Indonesia |
The
pyrolysis characteristics of Spirulina
platensis residue (SPR) with silica–alumina catalysts were investigated using thermogravimetric
analysis (TGA). The effects of differing amounts of catalysts on thermochemical
behavior and kinetics parameters (pre-exponential factor in Arrhenius equation
[A] and activation energy [Ea]) were studied. The experiment was carried out
from 30 to 1000? at a heating rate of 20?/min for the case of non-catalytic and
catalytic pyrolysis (silica–alumina). For the catalytic pyrolysis, also of
interest were the catalyst-to-SPR weight ratios of 1:1 and 1:2. The TGA curve
and differential thermogravimetric peak analysis results suggest that the use
of catalysts in pyrolysis (particularly at a catalyst-to-SPR weight ratio of
1:1) reduces both pyrolysis time and temperature range to 14.68 min and
230–555?, respectively. The kinetic parameters were then calculated in a
one-step global non-isothermal model and solved using a least squares method in
MATLAB. The presence of catalyst was able to reduce Ea to the lowest value from
41.10 kJ/mol (without catalyst) to 40.77 kJ/mol (weight ratio of 1:2)
and 39.46 kJ/mol (weight ratio of 1:1) in Zone 1. However, the increase of
catalyst quantity was not in line with the increase of reaction rate constant
(k) and resulted in reasonably low A of, respectively, 593.30, 406.31, and
266.37.
Activation energy, Catalytic pyrolysis; Pre-exponential factor; Spirulina platensis residue
By 2040, the world’s energy demand is estimated to have increased
by 56%, with fossil fuels still contributing about 80% of the required supply (Anggorowati et al., 2018). This expectation has
motivated an acceleration of the utilization of renewable sources, including
algae. Microalgae such as Spirulina
platensis have tremendous potential to be converted as a renewable fuel (Pradana et al., 2018). After the removal of lipid
content by extraction, biomass in the form of Spirulina platensis residue (SPR), used as a biofuel material, has
the
Generally,
a biofuel derived from the pyrolysis of SPR exhibits several deficiencies,
including the presence of high levels of oxygenous and nitrogenous compounds.
However, these disadvantages can be overcome through the use of a catalyst to
reduce the levels of oxygenous and nitrogenous compounds (Bui et al., 2016). One suitable catalyst for
upgrading the bio-oil is silica–alumina, which is widely used to support the
production of petrochemicals, chemicals, and energy. The Al2O3
can promote the formation of aromatic compounds, such as polycyclic aromatic
hydrocarbons. And with its low acidity, SiO2 can also help remove
oxygenated compounds and inhibit the formation of coke on the catalyst thanks
to the porous medium (Aho et al., 2013; Busca, 2019; Jamilatun
et al., 2019c). Jamilatun (2019c)
reported that the catalytic pyrolysis on SPR using a silica–alumina catalyst
(surface area of 240.553 m2/g, pore size of 3.3 nm,
average pore volume of 0.199 cm3/g, and SiO2/Al2O3
of 1.71) could reduce oxygenated compounds 37.47% (without catalyst) to 12.82%
(a decrease of 65.80%). Further investigation on the catalytic thermal
decomposition of SPR is crucially demanded to accelerate the development of
bio-oil production (Sunarno et al., 2018; Jamilatun
et al., 2019b; Jamilatun et al., 2019c). Its kinetic analysis and the
thermal decomposition mechanisms necessary to obtain pre-exponential factor (A)
and the reaction kinetics constant (k) from catalytic pyrolysis are the
critical tools for designing reactor developments for industrial-scale bio-oil
production (Li et al., 2013).
One
effective method of analyzing both thermal decomposition and reaction kinetics
is thermogravimetry (TG). Thermogravimetric analysis (TGA) has become a proven
technique for investigating the non-catalytic pyrolysis of algae, including Chlorella
sp., Tetraselmis suecica
(Kassim et al., 2014), Spirulina
extraction wastes (Li et al., 2013; Jamilatun et
al., 2017b), and Sargassum sp. (Kim et al., 2013). On the other hand, there is minimal research on catalytic
pyrolysis using the TGA method with microalgae raw materials, but Jamilatun et al. (2017b) reported that analysis of
thermal decomposition and pyrolysis reaction kinetics of SPR with TGA indicated
that the activation energy (Ea) for the heating rate of 20?/min for Zones 1 and
2 was 41.102 kJ/mol and 0.0001240 kJ/mol. However, there has been
almost no research work conducted on thermochemistry and kinetics of catalytic
pyrolysis reactions using TGA. For this reason, research on catalytic pyrolysis
of SPR needs to be developed, particularly with regard to pyrolysis
thermochemical behavior and kinetics.
Based on TGA
data, reaction kinetics can be approximated using a one-step reaction model
derived from the Flynn–Wall–Ozawa and Kissinger–Akahira–Sunose methods (Kassim et al., 2014; Quan
et al., 2016). In this method, a one-stage global single-reaction model
can be determined via various approaches, such as the distributed activation
energy model (DAEM), the iso-conventional method from Vyazovkin (Marriott et al., 2016), and nonlinear least
squares regression (Kim et al., 2013). To
the best knowledge of the authors, there is no previous study on biomass
kinetic reactions incorporating natural and straightforward processes. Hence,
as an alternative to establishing a one-stage global single-reaction model, a
reaction model using a least squares method and MATLAB simulation tools was
developed in this study. The data of catalytic thermal decomposition characteristics
of SPR in TGA are required to determine the reaction kinetics, and the kinetics
data are necessary to design the pyrolysis equipment for bio-oil production (Kim et al., 2013; Kassim
et al., 2014; Quan et al., 2016).
This paper discusses the characteristics
of thermal decomposition using a silica–alumina (SiO2/Al2O3)
catalyst, including the extent of the catalyst’s effect on SPR weight
reduction. This work uses TG and differential thermogravimetric (DTG) curves to
obtain the temperature ranges for Stage I (drying), Stage II (pyrolysis), and
Stage III (gasification). The kinetic reaction was calculated through a
one-step global non-isothermal model and solved with a least squares fitting
using MATLAB simulation.
This study
evaluated TG-DTG analyses as a feasible method for determining SPR pyrolysis
characteristics. The release of volatile matter, seen in the DTG curve as a
sharp peak, was observed in non-catalytic pyrolysis. In contrast, volatile
matter release was relatively similar in the presence of the catalyst. Based on
TG-DTG data, the presence of catalyst was able to reduce the pyrolysis time and
temperature range, with observed data of 230–570? (15.10 min); 230–565?
(15.07 min), and 230–555? (14.68 min) for the cases of no catalyst,
catalyst-to-SPR weight ratio of 1:2, and catalyst-to-SPR weight ratio of 1:1,
respectively. In the same case sequence, the kinetic study reported the
reduction of activation energy in Zone 1 as 41.10,
40.77, and 39.46 kJ/mol. However, the pre-exponential factor supports
also appeared lower, at 593.30, 406.31, and 266.37.
The reduction of activation energy due to the use of the catalyst is not in
line with the increase of k due to the quite low pre-exponential factor.
However, the rate in Zone 2 was not significantly affected because the values
of the kinetic parameters were rather small and relatively similar to one
another, in the range of 8.53×10?5–1.42×10?4 kJ/mol and 0.0505–0.0488 for each activation energy and
pre-exponential factor, respectively.
The
authors are very grateful to the Ministry of Research and Technology/National
Agency for Research and Innovation of the Republic of Indonesia for financial
support.
| Filename | Description |
|---|---|
| R3-CE-2967-20200504164716.pdf | Cover Letter |
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