Kinetic analysis of Oil Palm Empty Fruit Bunch (OPEFB) pellets as

Feedstock for Pyrolysis

Bemgba Bevan Nyakuma, Arshad Ahmad, Anwar Johari, Tuan Amran Tuan Abdullah,
Olagoke Oladokun, Aliyu Bello, Habib Alkali, Saeed Isa Ahmed
Institute of Hydrogen Economy, Universiti Teknologi Malaysia
81310 Skudai, Johor Bahru Malaysia
Phone: +60133337635
Email: bbnyax1@gmail.com,bnbevan2@live.utm.my
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ABSTRACT

The thermal behaviour and decomposition kinetics of pelletized oil palm empty fruit bunch (OPEFB) was
investigated in this study using thermogravimetric analysis (TGA). The OPEFB pellets were heated from
room temperature to 1000 C at different heating rates; 5, 10 and 20 C min-1 under inert atmosphere.
Thermal degradation occurred in three steps; drying, devolatization and char decomposition. Subsequently,
the Popescu method was applied to the TG/DTG data to determine the kinetic parameters of the OPEFB
pellets. The activation energy, E, for different degrees of conversion, = 0.05 to 0.7 are 36.60 kJ/mol to
233.90 kJ/mol with high correlation R2 values. In addition, the drying and decomposition of lignin reactions
displayed lower E values compared to the devolatization characterized by high E value of 233 kJ/mol at
= 0.2. This indicates that the devolatization process is slower and requires higher energy requirement to
reach completion than the other stages of thermal decomposition of the fuel under inert atmosphere.

Keywords: decomposition, kinetics, oil palm, empty fruit bunch, pyrolysis

1. INTRODUCTION

The inefficient disposal and management of waste in the Malaysian oil palm industry
has resulted in increased environmental pollution, greenhouse gas (GHGs) emissions, and
burden on the life cycle of palm oil production. In spite of this, lignocellulosic oil palm waste
(OPW) can be converted into solid, liquid and gaseous biofuels. The potential of OPW as a
renewable feedstock for clean biofuels production has been highlighted in literature [1-4].
However, the valorisation of OPW for energy applications is currently hampered by the
poor fuel properties [5], low conversion efficiencies [6] and operational problems such as
agglomeration [7]. The effective, efficient and sustainable utilization of biomass resources for
energy applications can be improved by characterization and pre-treatment processes. Hence,
knowledge of the thermochemical properties of lignocellulosic biomass resources is vital
particularly in the design, optimization and scale up of future biomass conversion systems.
Therefore, this study is aimed at investigating the thermal behaviour and decomposition
kinetics of oil palm empty fruit bunch (OPEFB) pellets using a thermogravimetric analyser
(TGA). This will augment current scientific knowledge on thermochemical conversion of
OPEFB currently hampered by operational problems [8].

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 2. EXPERIMENTAL

The OPEFB pellets were procured from a local oil palm mill in Kota Tinggi, Johor
Malaysia. The pellets were pulverised in Panasonic Dry MillerTM and sieved using a RetschTM
analytical sieve to obtain homogenous particles below 250 m in size. Ultimate analysis was
determined using the LECO CHNS 932 elemental analyser according to ASTM D5291. The
proximate of the OPEFB was determined using standard ASTM techniques E871, E872 and
D1102 for determining moisture content, volatiles and ash respectively. The tests were
repeated at least three times to ensure the reliability of the runs. The fixed carbon content of
the fuel was determined by difference. For each TGA run 8-10 mg of powdered OPEFB
pellets was placed in an alumina crucible and heated from 30-1000 C in a Netzsch 209 F3
TG Analyser at 5 C/min, 10 C/min and 20 C/min heating rates using nitrogen (99.99%)
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N2 (flowrate 50 ml/min) as purge gas. The TG/DTG data was deduced to investigate the
thermal behaviour and decomposition kinetics of the OPEFB pellets using the Popescu
method [9]. The kinetic method has been described and successfully applied to biomass
materials [10-12]. Hence the method was applied in this study to determine the activation
energy E, conversions, = 0.05 - 0.7 of the OPEFB pellets.
The rate of solid state thermal decomposition of the OPEFB pellets can be described
by the modified Arrhenius equation expressed mathematically as;

= exp ( ) () (1)

Where, d/dt is rate of conversion, t - time; A - pre-exponential or frequency factor; E -
activation energy; R - universal gas constant, f() is the reaction model. At constant heating
rate, , given by the relation, dT/dt, can be substituted into Eq.1;

= exp ( ) () (2)

By integrating Eq.2, we can obtain the integral form for the dependence function of
conversion f() denoted by G() expressed as;


( ) = = ( ) (3)
0 () 0 ()
Eq.3 is the general equation used to describe the temperature dependence of the kinetic
parameters during solid state thermal decomposition of biomass species. Hence, it is the basis
for numerous isoconversional models such as the (KAS) Kissinger-Akihara-Sunose [13] (Eq
4) from which the Popescu method is derived [12].

ln ( ) = ln ( ) = (4)
2 ()
The generalised expression for the Popescu method [9, 10], Eq.3 can be rewritten for the
degrees of conversion am, and an undergoing thermal conversion at temperatures Tm, and Tn
respectively;

1 T
() = = () = () (5)
() T
The terms (H)Tmn, and T are defined by Eq. 6-7 respectively;

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() = ( ) ( ) (6)

+
= ( ) (7)
2
Consequently, the final equation for the Popescu method can be obtained by integrating Eq.
4 at temperatures Tm and Tn for degrees of conversion am and an respectively.

ln ( ) = ln ( ) (8)
()
Therefore the activation energy E, can be deduced from the slope of the plot of In [ / (Tn-
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Tm)] vs 1/T for the decomposition of the biomass during thermal analysis.

3. RESULTS AND DISCUSSION

3.1 Chemical Fuel Properties

The heating value, ultimate and proximate analyses for OPEFB pellets are presented in Table 1.
The oxygen and fixed carbon were obtained by diffrence from the ultimate and proximate analysis
repsectively. The ultimate analysis is presentened in dry ash free (daf) basis while proximate and
heating value are reported in as received (a.r) basis.
Table 1: Chemical fuel properties of OPEFB Pellets.
Carbon C 49.44
Hydrogen H 6.57
Ultimate Analysis Nitrogen N 1.38
(wt %) daf basis Sulfur S 0.05
Oxygen* O 57.16
Moisture M 8.17
Proximate analysis Volatiles V 71.83
(wt % ar basis) Fixed Carbon* F 15.44
Ash A 4.56
Heating value (MJ/kg) Higher Heating Value HHV 17.57
The elemental C, H, O content for biomass generally range from; 42-71 %, 3-11 % and 16-49 %
respectively. The elemental composition of OPEFB pellets presented in Table 1 is in good
agreement with reported literature values [14]. The study by Vassilev et al., (2010) also reveals that
biomass N content ranges from 0.1-12 % and 0.01-2.3 % for S which suggests that the reported
OPEFB properties are within the acceptable limits. Furthermore, it also indicates that the fuel has
low susceptibility to NOx and SOx emissions during thermal converison.
The volatiles and fixed carbon content of biomass are generally within 48-86 % and 1-38 %
respectively [14]. Since volatiles and fixed carbon comprises condensable and noncondensable
matter [15] namely CO, CO2, H2, moisture and tars [16], we can predict that thermal conversion of
OPEFB pellets will yield reasonable solid, gaseous, and liquid products.
The heating value of the OPEFB pellets (17.57 MJ/kg) indicates the fuel contains sufficient
calorific value for utilization as a solid biomass fuel (SBF) for future thermochemical energy

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 applications. Furthermore, its low moisture and ash content is vital for efficient fuel conversion
and minimal operating problems such as agglomeration and slagging [17] in gasifiers and biolers.

3.2 Thermal Analysis of OPEFB

Figures 1-2 present the TG/DTG curves for OPEFB pellets indicating weight loss (mass loss
fraction) and derivative weight loss under inert atmosphere. The curves show the typical inverted
S-shaped temperature depedent weight loss phenomena typically observed for the decomposition
of biomass materials during thermal analysis.
1.1
1.0
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0.9
0.8
Mass Loss Fraction (%)

0.7 5 C/min
0.6 10 C/min
0.5 20 C/min
0.4
0.3
0.2
0.1
0.0
25 100 175 250 325 400 475 550 625 700 775 850 925 1000
Temperature ( C)

Figure 1: TG curves for OPEFB pellets.

-2
Derivative Weight Loss (%/min)

-4

-6
5 C/min

-8 10 C/min
20 C/min
-10

-12

-14
25 100 175 250 325 400 475 550 625 700 775 850 925 1000
Temperature (C)

Figure 2: DTG curves for OPEFB pellets.

In addition, we can observe the curves shifted to the right with increasing heating rate from 5 C
to 20 C during thermal analysis. This can attributed to the thermal lag resulting from the thermal
resistance between the reacting and evolved species which occurs at higher heating rates during

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 thermal analysis of biomass samples. This observation has been described by other researchers in
literature and is this is considered as classic behaviour of biomass materials during in thermal
analysis [18, 19].The DTG curves in Fig. 2 also displayed the temperature dependency of the
thermal decomposition process (TDP) observed in the TG curves of the sample with increase in
heating rate. In addition, analysis of the curves also indicate that the TDP is a 3-step occurrence
involving the loss of moisture or drying from (30-175 C), active devolatization or loss of volatiles
from (175-400 C) and char degradation (400-1000 C) denoted by the long tailing in the DTG
curves. Similar trends have been reported for biomass samples in literature [20, 21].

3.3 Kinetic Analysis of OPEFB

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The Popescu method was used to deduce the activation energy, E, from the slope of the plot
of In [ / (Tn-Tm)] vs 1/T presented in Figure 3 for the degrees of conversion am and an at
temperatures Tm and Tn for respectively.
1.0
0.05
0.5 0.10

0.0 0.20

0.30
-0.5
0.40
-1.0
0.50
-1.5
In[/[Tn-Tm)]

0.60

-2.0 0.70

-2.5

-3.0

-3.5

-4.0

-4.5
0.0010 0.0012 0.0014 0.0016 0.0018 0.0020 0.0022 0.0024 0.0026
1/T (K-1)

Figure 3: Regression plots for OPEFB pellets.

The values 0.05 -0.70 represent the degree or extent of conversion of the OPEFB pellets at 5
% to 70 % during thermal-kinetic analysis. It is important to state that values above 0.7 (70 %
conversion) have been customarily excluded due to low correlation (R2). The activation energy,
E was widely distributed for the degrees of conversion, an, am as presented in Table 2. The
values of E ranged from 36.60 kJ/mol to 233.92 kJ/mol with high correlation (R2) values. The
results highlight the influence of temperature on the kinetics of OPEFB pellets
decomposition.

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 Table 2: Activation Energy, E, of OPEFB from Popescu Method
Heating Rate, R2 E (kJ/mol)
0.05 0.9980 59.51
0.10 0.9985 131.25
0.20 0.9981 233.92
0.30 0.9657 169.97
0.40 0.9565 125.93
0.50 0.9055 164.24
0.60 0.8844 181.42
0.70 0.5225 36.60
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The highest E was 233.93 kJ/mol at the degree of conversion = 0.2 during the active
devolatization or loss of volatiles from 175-400 C. The reported E values for lignin (250-550
C), hemicellulose (250-350 C) and cellulose (300-430 C) are 80, 100 and 200 kJ/mol [12].
Hence it will appear the predominant reaction during the thermal analysis of OPEFB pellets
is the active devolatization or cellulose decomposition. However the overlapping temperature
ranges and reactivity of the lignocellulosic biomass components mean that lignin and
hemicellulose also undergo decomposition concurrently at low temperatures [22].
The lowest E values of were 59.51 kJ/mol at = 0.05 for drying and 36.60 kJ/mol at
= 0.70 for lignin decomposition. This suggests that the drying and devolatization reactions
require minimal energy to occur rapidly compared to active devolatization process during
thermal analysis. Hence, we can infer that active devolatization of the OPEFB pellets is the
slow reaction or rate determining step during thermal degradation.

4. CONCLUSION

The thermal kinetics and decomposition behaviour of oil palm empty fruit bunch (OPEFB)
pellets was investigated at different heating rates under non-isothermal inert conditions.
Thermal analysis revealed the widely reported three-step-reaction process; drying,
devolatization and lignocellulosic char decomposition. Thermal kinetics was evaluated using
the Popescu method, a modified form of the Kissinger-Akihara-Sunose (KAS) method to
determine the kinetic parameters of the OPEFB pellets. The average activation energy, E, for
overall decomposition of the fuel was 137.86 kJ/mol. In addition, the drying and
decomposition of lignin reactions displayed lower E values compared to the devolatization
stage which can be considered as the rate determining step of the process.

ACKNOWLEDGMENT

The authors will like to acknowledge the financial support of the Ministry of Education
Malaysia for the Long Research Grant Scheme (LRGS VOT No. 4L817). The contribution of
Syie Liung Wong, Muhamad Faizal and Dr Ahmad Romli of POCREST, Universiti Teknologi
MARA, Shah Alam is gratefully acknowledged.

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