J. Nig. Soc. Phys. Sci. 4 (2022) 205–213

Journal of the
Nigerian Society

of Physical
Sciences

Analysis of Adenanthera pavonine L. (Febaceae) Pod and Seed
as Potential Pyrolysis Feedstock for Energy production

Olugbenga Oludayo Oluwasina∗

Department of Chemistry, Federal University of Technology Akure, Nigeria

Abstract

Though countless possible bioenergy feedstocks are available, the lack of information on their characteristics has made them unusable for in-
dustrial purposes. This study revealed the bioenergy potential of seed and pod of Adenanthera pavonine by analyzing their physicochemical,
ultimate, proximate, kinetic, thermodynamic, thermal, and higher heat value. The seed presented 19.90%, 2.12%, 24.40% and 14.73% cellulose,
hemicellulose, lignin and extractive respectively, while the pod has 21.35%, 25.15%, 23.50% and 11.63%. From the proximate analysis the pod
has higher volatile matter (92.79%), and fixed carbon (1.40%), while the seed has higher moisture (6.36%), ash (0.84%), and higher heat value
(18.63 MJ kg−1). The kinetic and thermodynamics results present the seed with Ea 23.73 kJmol-1, ∆H 14.06 kJmol-1, ∆G 10.74 kJmol-1 and ∆S
-78 Jmol-1, while the pod has 21.3 kJmol-1, ∆H 12.20 kJmol-1, ∆G 10.98 kJmol-1 and ∆S -83 Jmol-1. The probable energy blockade between
Ea and ∆H for the seed and pod was 9.72. The high value of H: C and low O: C, with the higher heating values recorded for the pod and seed,
presented them as better biofuel candidates. The study results have supplied necessary information for the industrial utilization of Adenanthera
pavonine seed and pod as valuable feedstocks for bioenergy conversion.

DOI:10.46481/jnsps.2022.555

Keywords: Adenanthera pavonine, Composition analysis, Ultimate analysis, Proximate analysis, Kinetic, Thermodynamics

Article History :
Received: 30 December 2021
Received in revised form: 25 February 2022
Accepted for publication: 25 Februrary 2022
Published: 29 May 2022

c©2022 Journal of the Nigerian Society of Physical Sciences. All rights reserved.
Communicated by: E. A. Emile

1. Introduction

An increase in world population coupled with rapid indus-
trialization and urbanization is causing a reduction in fossil fuel
energy resources. Also, the negative environmental greenhouse
gas effect of fossil fuel is calling for alternative replacement for
fossil fuel energy.

Plant biomass is renewable, abundant, and easily adaptable
is being considered as the capable replacement for fossil fuel

∗Corresponding author tel. no:
Email address: oooluwasina@futa.edu.ng (Olugbenga Oludayo

Oluwasina )

energy. It can supply a hygienic, renewable, dependable, and
low-carbon print fuel. About thirteen percent of the world’s en-
ergy can be derived from biomass, is converted directly to heat,
biofuels, and value-added chemicals through various reaction
pathways [1].

Nevertheless, using biomass as a raw material for fuel gen-
eration has its drawback, there are numerous character differ-
ences between and within various biomass types and species.
Therefore, knowledge of the physicochemical properties and
the energy value of biomass are very vital for its proper utiliza-
tion [2]. The chemical constituent of biomass such as mois-
ture, cellulose, lignin, hemicellulose, extractive, and ash play
different vital roles in determining the suitability of the mate-

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Oluwasina / J. Nig. Soc. Phys. Sci. 4 (2022) 205–213 206

rial for particular end-use. The moisture content of biomass
can affect the higher heating value if too high and also impact
negatively the bio-oil properties. The elemental composition of
fuel-derived biomass is very important for the control and pre-
vention of ash fouling and slag formation which could affect
thermochemical processing delivery pipes. Biomass with high
cellulose or hemicellulose content would produce a higher yield
of bio-oil, while those with higher lignin content will give rise
higher yield of char [3].

To obtain the inherent energy content of biomass, a ther-
mochemical processing system is needed, this cannot be con-
structed without the knowledge of its thermal behaviour and
chemical composition [4]. Thus, information on the pyrolytic
behavior of the biomass from its thermogravimetric (TG) char-
acterization is essential before the industrial utilization in a ther-
mochemical plant. Parameters such as rate of biomass decom-
position and the activation energy valuable for engineering de-
sign of thermochemical conversion unit are obtained from TG
using Coats and Redfern model [5]. Thermodynamic parame-
ters; entropy (∆S), enthalpy (∆H), and Gibbs free energy (∆G)
are useful to verify the visibility of the pyrolysis occurrence,
operation condition, and possible products

Proximate analysis is a valuable means of defining and en-
visaging the heating values of biomass, it helps to reveal the
fuel behavior of the biomass at various stages during combus-
tion [6]. Whereas, the biomass fuel efficiency and cleanness
can be predicted using both the proximate and ultimate analysis
[7]. Higher heating value (HHV) is used to quantify the energy
worth of biomass fuel. Experimentally, HHV of biomass fuel
can be determined using a bomb calorimeter, however, because
of the cost and time-consuming nature of the procedure, vari-
ous authors have utilized data obtained from the proximate and
ultimate analysis to determine the HHV of different biomass
through the use of empirical models [8-12].

Adenanthera pavonina L. is a wild underutilized plant that
can be exploited for firewood, shade, ornamental, medicinal,
and dyeing purposes [13]. The ability of Adenanthera pavonine
as low-cost biosorption for Pb (II) and Cd (II) from wastewa-
ter has been demonstrated and it was reported that the seed has
a good sorption capacity for the two metallic ions [14]. Ex-
tracted galactomannan from Adenanthera pavonina L has been
reported as a good binder in cement-based hydroxyapatite com-
posite [15]. Medicinal importance of the various parts of the
plant has been documented by various authors; anti-inflammatory
[16], anti-blood pressure [17], and anti-diabetic [18].

Due to the lack of data on the biofuel potential of pod and
seed of Adenanthera pavonine, this research work is aimed at
the exhaustive analysis of the pod and seed of Adenanthera
pavonina to reveal their bioenergy possibility and provide data
for designing a thermochemical conversion system for the in-
dustrial utilization.

2. Material and Method

2.1. Material
Samples were obtained from Adenanthera pavonine tree at

the Federal University of Technology, Akure, Ondo State, Nige-

ria. Contaminants were sorted out, the seeds were removed
from the pods and the materials were sundry (72 h). The ma-
terials were pulverized and sieved to obtain 450 m particle size
and then stored in an airtight container at room temperature.

2.2. Extractive free sample

A biomass (B1) was Soxhlet extracted (4 h) serially with
(1: 2) ethanol (985%): toluene, ethanol (4 h), distilled water
(500mL x 3), then dried (105 oC) to a constant weight (B2)
[19]. Percentage extractive was calculated thus after a triplicate
experiment:

Extractive content (%) =
[
(B1 − B2)

B1

]
× 100 (1)

2.3. Acid-insoluble lignin

To the extracted biomass (E) was added sulphuric acid (72%,
15 mL) at 20 ◦C (2 h). The experiment was stopped by adding
deionized water (560 mL), before heating (95 ◦C, 4 h) and then
allowed to cool (24 h). The filtered was obtained as acid-soluble
lignin and the solid as the acid-insoluble lignin (washed to pH
7) after oven-dried to a known weight (L) [20]. A triplicate
experiment was done and acid-insoluble lignin was calculated
thus:

Klason lignin, (%) =
L × 100

E
(2)

2.4. Acid-soluble lignin

To acid-soluble lignin filtrate volume (V = 575 mL) was di-
luted with sulphuric acid (3%) and the ultraviolet absorbance
(AB) read at 205 nm, with sulphuric acid (3%) being the ref-
erence sample [21]. Lignin content in the filtrate (B in g/1000
mL) was calculated as follows:

B =
AD
100

(3)

Where: D= The dilution factor of the filtrate, 110 = Absortiv-
ity or extinction coefficient. The acid acid-soluble lignin was
calculated as follows:

Lignin (%) =
110BV
1000w

(4)

2.5. Holocellulose

A mixture of extractive free biomass (We), distilled water
(150 mL), glacial acetic acid (0.2 mL), and sodium chlorite (1
g) was subjected to heat treatment (70 ◦C). The procedure was
repeated three times but without the addition of distilled water
and biomass. The solid sample was washed free of chlorine,
oven-dried (105 oC) to weight (Wh) [22]. A Triplicate exper-
iment was performed and the holocellulose content was deter-
mined as:

Holocellulose content (%) =
[

we
wh

]
× 100 (5)

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Oluwasina / J. Nig. Soc. Phys. Sci. 4 (2022) 205–213 207

2.6. Alpha-cellulose
The obtained holocellulose was treated with sodium hy-

droxide (17.5%, 50 mL, 20oC), distilled water (50 mL) was
added after 29 min. The solid particle obtained was washed
to neutral pH with deionized water [22] and then oven-dried
(105 oC) to constant weight (w00). A triplicate experiment was
done and cellulose was determined with the following formula:

Cellulose (%) =
[

w9
woo

]
× 100 (6)

2.7. Instrumental analysis
Perkin Elmer STA 6000, was used for the determination of

the sample proximate composition (moisture content, volatile
matter, ash content, and fixed carbon). Scanning Electron Mi-
croscope (SEM) coupled with-Energy Dispersed X-ray (EDX)
(FEI FIB/SEM Nova 600 Nanolab) was used for the morpho-
logical characteristic and elemental composition of the samples
using the ash component. Thermogravimetry analysis (TG/DTG)
was conducted (TGA TA STD Q6000) in a nitrogen atmosphere,
flow rate 20 mL min−1 at a temperature (30 and 900 oC), and
heating rate 10 oC min−1, about 10.0 mg sample was used for
the thermal characterization. Perkin Elmer CHNS was em-
ployed for ultimate analysis determination of percentage car-
bon, hydrogen and sulfur content, while oxygen (%) was cal-
culated by difference {(O =100 – (C+H+N+S+Ash)}[23]. The
H/C and O/C ratios were determined using empirical methods
[24, 25] as follows:

H
C

=
number of H atoms
number of C atoms

=
%H/1
%C/12

(7)

O
C

=
number of O atoms
number of C atoms

=
%O/16
%C/12

(8)

2.8. Higher heating value
Higher heating value (HHV) or gross calorific value were

using the empirical formula [26] as follows;

HHV (M J/kg−1) = 0.0877L + 16.4951 (9)

2.9. Kinetic and thermodynamic parameters
Modified Coats and Redfern model (Equation 10) [5] was

employed for the determination of the activation energy (Ea),
pre-exponential factor (A), and Regression coefficient (R2) through
the graph plot of ln [ln (1- x)] against 1000/T. Thermodynamics
parameters such as entropy (∆S), enthalpy (∆H), and Gibbs free
energy (∆G) were calculated using equations (11-14) [27,28].
Different factors such as Boltzmann constant KB (1.381 x10−23

J/K), Plank constant h (6.626 x 10−34 J/s), and TG peak tem-
perature (Tm/K) are usually used in the calculation and other
necessary values during the calculation are obtained from the
TG data.

ln [−ln (1 − x)] = ln
ART 2

βEa
−

Ea
RT

(10)

A =

[
β∗ E x p

(
E

RTm

)]
RT 2m

(11)

Figure 1: Percentage composition of biomass

∆H = Ea − RT (12)

∆G = Ea + RTmln (KBTm/hA) (13)

∆S = ∆H − ∆G/Tm (14)

3. Results and Discussions

3.1. Composition of biomass

The seed and pod of Adenanthera pavonine displayed dis-
tinct characters. The extractive results revealed 13.73 % for
the seed while the pod recorded 11.63 %. This is expected be-
cause the chemical composition of biomass can be influenced
by the nature of such material. It has been reported that both
saturated and unsaturated fatty acids are abundant in Adenan-
thera pavonine seed [29]. The percentage extractive presented
in this study is higher than 7.78% and 9.75%, but lower than
13.82% to 32.86% reported for different date palm residue [30].
The high extract content of the seed suggests that it can sup-
port biomass burning and ignition ability, an added advantage
if used in composite briquette compounding. The pod recorded
21.14% cellulose and 23.50% hemicellulose, both are higher
than the 19.90% and 21.12% for cellulose and hemicellulose
of the seed. On the other hand, the 24.40% lignin content of
the seed was higher than 23.50% of the pod. The cellulose
content of the seed and pod are lower than 45-50 % for hard-
wood -and soft wood-cellulose [31], but compared favourably
with 12-29% reported for lignocellulosic residue [32], while the
hemicellulose was in agreement with 15-35% for hardwood and
20-31% for softwood [31]. However, the lignin content of both
the seed and pod was higher than 11-22 reported for lignocel-
lulosic biomass [32]. It can be inferred from the results of the
hemicellulose and cellulose of the pod and seed that biomass
will experience faster thermal degradation, thus saving energy
cost during pyrolysis, though at the expense of higher heating
value that the lignin would have supplied.

3.2. Proximate analysis of biomass

The pod has a lower moisture content of 5.22% against
6.36% of the seed. The higher moisture content of the seed

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Oluwasina / J. Nig. Soc. Phys. Sci. 4 (2022) 205–213 208

might be due to its high extractive content (fatty acid, resin,
gum) which could have prevented the evaporation of bond wa-
ter.
The reported moisture contents (pod and seed) were lower than
8.00% [33] and 7.02% [34] for Lantana camara by different au-
thors. The low moisture content of the pod agreed with the
low value reported for the pod Acacia mangium amongst all its
various parts [35]. The moisture contents of the pod and seed
are lower than fifteen percent recommended for pyrolysis re-
quired biomass [36]. Higher moisture content is expected to
engineer microbial degradation, which will invariably affect the
fuel quality of the biomass. Thus, the seed and the pod would
be good fuel oil-producing feedstock [37]. High volatile matter
is desirable in pyrolysis feedstock because it would aid igni-
tion and support the biomass burning ability. After all, they
are expected to produce a high quantity of bio-oil [38]. There
is no significant difference between the volatile matter of the
seed (91.79%) and pod (92.79%), suggesting that those materi-
als would have good ignition ability. The higher volatile matter
reported in this study was not an isolated case, higher volatile
values have been reported for the pod of Acacia mangium [35]
and Bauhinia monandra [39]. The volatile matter the seed and
pod here reported is higher than 69.82 to 74. 85% for var-
ious part Acacia mangium [35], 74.30% to 87.50% for date
palm [30]. The difference in the volatile matter of the differ-
ent biomass could be linked to the plant types, nature of the
biomass, and the state of the biomass before analysis. The ox-
ides of the elements present in the biomass represent the ash
content, which can be determined as the solid inorganic com-
ponent after the thermal degradation of the biomass. The worth
and durability of thermochemical products and plant-unit are
mostly influenced by the ash feedstock content. Slag devel-
opment during the thermochemical process would corrode the
system [4], the corrosion indirectly affects the quality and quan-
tity of the biofuel, increasing the energy need and cost of system
maintenance. Thus, feedstock with minima ash content is desir-
able for thermochemical conversion. It has been affirmed that
biomass feedstock with ash values ranging from 1.41 to 2.69%
is a good candidate for bioenergy utilization [35]. Hence, ash
values of 0.84% (seed) and pod 0.59% (pod) make these ma-
terials better feedstock and it is envisaged that the associated
ash problem of biomass would be eliminated or minimized if
these materials are utilized as thermochemical feedstock. The
pod and the seed ash values are lower than 4.5 to 10.5% switch-
grass [40] and 2.68% grapevine pruning, 1.94% olive pruning,
and 2.25% riverbank residue [41]. The ash differences of the
various biomass can be ascribed to various factors such as soil
type, ecological reason, plant types, and part. The thermochem-
ical undecomposed part of the biomass is the fixed carbon [35],
which can be employed in biochar preparation. However, low
biochar feedstock is preferable for thermochemical biofuel ap-
plication because of the expected high bio-oil yield. The two
materials examined in this study; pod and seed presented 1.01%
and 1.40% fixed carbon respectively, probably the reason for
the high volatile matter content of those materials. It is there-
fore assumed that the pod and seed of Adenanthera pavonine,
would be a good candidate for bioenergy production. The fixed

carbon of this study is very low compared with 14.47 to 18.31%
from different parts of Acacia mangium [35], but are higher
than 0.34% and 0.623% for Delonix regia seed and pod.

From the HHV analysis of the biomass using [26] formula
for non-wood lignocellulosic fuels. It was revealed that the pod
and the seed have higher but different values; the seed has 18.63
HHV values, while the pod recorded 18.56. The higher value
of the seed could be the effect of its high lignin and extractive
values, both of which have been documented to increase HHV
[26]. The HHV reported in this study are lesser than 20-25
MJ kg-1 of sweet sorghum [42], but are higher 15.00 MJ kg-
1 for camel grass [43], 15.10 MJ kg−1 of para grass [44], and
17.20 MJ kg-1 of A. donax [45], all of which are notable fuel
biomass. Thus, the seed and pod of Adenanthera pavonine can
be adjudged to be good energy biomass.

3.3. Ultimate analysis of biomass

The CHNS carbon, hydrogen, sulphur, and oxygen values
for the seed are 38.26%, 6.30%, 1.92%, and 52.68% against
43.01%, 5.785. 1.63% and 48.99% of the pod. All the ob-
tained values are in agreement with literature values for various
biomass [26]. The pod is richer in carbon and oxygen, while the
seed is richer in hydrogen and sulphur. The fuel potential of the
biomass can be predicted from carbon, oxygen, and hydrogen,
making those elements important in the biomass thermochem-
ical process. The knowledge of sulphur content would help in
preventing possible environmental pollution from its gaseous
products. The H: C ratio of 1.97 and 1.61 were recorded for
the seed and the pod respectively. These values are within the
range of 1.46 to 2.18 for different non-edible biomass [46] and
1.54 to 1.67 for various walnut shells [47]. Also, 1.03 and 0.85
recorded for the O: C ratio is within the range of 0.72 to 0.99
for different date palm residues [30]. The higher H: C fraction
and lower O: C fraction of the pod and seed, indicate them as
better biofuel candidates [48]

3.4. Elemental analysis of biomass

The mineral content of biomaterial for bio-energy research
is very essential, considering the negative effect those metals
could have on the desired products and the processing unit. The
EDX analysis of the ash presents the presence of K, Na, Ca,
Mg, P, and O in the seed while Na was not detected in the seed,
Si and other elements in the seed are detected. The seed has
a higher content of Na (1.330), Mg (7.36), and P (1.81), while
the pod has K (44.71), and Si (0.93). The low level of Silica in
the pod and its absence in the seed, coupled with the absence of
heavy metals in both the seed and the pod signifies the safeness
of these materials as a good feedstock for bioenergy production.
The ash is rich in essential minerals (K, Na, Mg, and P) for plant
growth; therefore, the ash can be utilized as a biofertilizer.

However, alkali earth metals are known to induce in-situ
reactions such as cracking which often led to low oil yield and
high gas production [49]. Also, those metals can inhibit micro-
organisms if those biomasses are used biochemical for purposes
[50]. Hence, there is a need for pretreatment of the biomass to
reduce the metal content during thermochemical conversion

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Oluwasina / J. Nig. Soc. Phys. Sci. 4 (2022) 205–213 209

Figure 2: Proximate analysis of biomass (Fixed carbon calculated by difference)

Figure 3: Ultimate analysis of biomass (O* Calculated by difference)

3.5. Thermogravimetry analysis

The major chemical composition of biomass is cellulose,
hemicellulose, lignin, extractive, and ash. The chemical com-
positional similarity and the proximity in the proximate, ulti-
mate and elemental analyses of the two analyzed materials in
this study, could be responsible for the sameness of their dif-
ferent TG/DTG curves. The curves presented the initial weight
loss from zero to 150 ◦C ascribed to moisture loss. The sec-
ond weight loss (150 - 400 ◦C) is due to the decomposition of

hemicellulose and cellulose. While the pod presented a single
peak at this temperature, the seed presented about two peaks,
which suggests that there is hemicellulose/cellulose decompo-
sition overlap in the pod but this was not so in the seed that
presented two distinct peaks as revealed by the DTGA. Lignin
being thermally stable than cellulose and hemicellulose were
the last to be degraded. This experienced a long duration from
400 - 900◦C. The seed experienced higher degradation energy
at 357.36 ◦C, while that of the pod was at 353.28◦C, indicating

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Oluwasina / J. Nig. Soc. Phys. Sci. 4 (2022) 205–213 210

Figure 4: TG/DTG of pod (a) and seed (b)

Table 1: EDX Analysis result

Element (%) Seed Pod
Potassium 36.66 44.71

Sodium 1.33 Not detected
Calcium 6.11 4.5

Magnesium 7.36 1.98
Silica Not detected 0.93

Phosphorous 10.81 1.00
Oxygen 37.73 46.83

that higher energy is required for degradation of the seed.

3.6. Morphology Characterization

The SEM investigation revealed a noticeable variance in the
morphology of the seed and the pod of Adenanthera pavonine.
When the pod appeared as a smooth surface, ball-like, and not
too densely packed material, the seed presents a rough surface,
flat-like, densely packed, and irregular shape material. Though,
the two materials are composed of the same chemical compo-
sition the differences in the amount present and their location
could have influenced the surface morphology

3.7. Kinetic and thermodynamics

Activation energy signifies the minimum energy that biomass
must acquire before its main constituents (such as cellulose,
hemicellulose, and lignin) can be converted to various pyrolytic
products such as gas, liquid, and solid char. The higher acti-
vation energy (23.78kJmol−1) of the seed over that of the pod
(21.92kJmol−1) can be linked to its high lignin content. Ther-
mally lignin is stable than cellulose and hemicellulose, and higher
energy is required in breaking the lignin bond. The high Ea of
the seed agreed with the literature finding that the higher Ea
of Kaner seed was as a result of its volatile constituents such as
fatty acid [51]. Ea observed in this study are lower than 221-229

kJ mol−1 (rice husk) [52] and tobacco residue [53]. The differ-
ence between the Ea and ∆H values for the seed and pod was
found to be 9.72kJmol−1 which is higher than approximately 5
kJmol−1 reported to signify fastness in converting the biomass
to products [54]. The higher Ea of the seed can be supported
from the thermal analysis in which the seed’s highest degrada-
tion temperature was higher (357.36 ◦C) than that of the pod
(353.28 ◦C), revealing that much energy was consumed by the
seed in breaking its components.

The energy released by biomass during pyrolysis is quan-
tified by Gibbs free energy and values of 10.74 kJmol-1 (seed)
and 10.98 kJmol−1 (pod) suggest a non-spontaneous process.
The result implies that the pod will supply more bioenergy than
the seed. The values obtained in this study were lower than
those reported by [54]. The results of ∆H follow the same pat-
tern as that of Ea, the seed has the higher value. Though, the
positive ∆H predicts that heat would be absorbed during the
breaking down of the precursor components. The lower ∆H
value of the pod indicates that its products can be easily sep-
arated during pyrolysis. The higher ∆H recorded by the seed
might be associated with its chemical composition because it
contains high lignin and extractive contents. Both of which will
require extra energy in bond breaking. The ∆H reported in this
study was lower than those reported for Kaner seed, flaxseed,
and microalgae with a 5 to 20 ◦C/min heat rate [51]. The entropy
∆S reflects the disorderliness the biomass precursor underwent
under chemical or physical treatment owing to thermal treat-
ment [55]. The higher ∆S of the seed implies that it would be
more reactive and require less reaction time to reach the activa-
tion complex, while the pod will experience the opposite [28].
Undoubtedly, The reactivity of the seed is not unconnected with
its higher Ea and ∆H.

4. Conclusion

The bioenergy ability of the seed and pod of Adenanthera pavo-
nine has been evaluated. The chemical composition of both ma-

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Oluwasina / J. Nig. Soc. Phys. Sci. 4 (2022) 205–213 211

(a)

Figure 5: SEM of the pod (a) and seed (b)

Table 2: Kinetics and thermodynamics results

Seed pod Ea-∆H
Ea 23.78 kJ mol−1 21.92 kJ mol−1 9.72
A 0.01648985sec 0.0106400833sec
R2 0.9432 0.9433
∆S -79.82 J mol−1 -83.466 J mol−1
∆H 14.06 kJ mol−1 12.20 kJ mol−1 9.72
∆G 10.74 kJ mol−1 10.98 kJ mol−1

terials revealed the presence of lignocellulose constituents that
can support biomass-bioenergy. The ultimate analysis showed
that the materials have a high volatile matter, suggesting their
good ignition ability and they could be used as composite for

biomass with low ignition prowess. The high heating values
recorded for the pod and seed were in tandem with the good
bioenergy characteristic as suggested by the ultimate analysis,
compositional analysis, and higher H: C fraction and lower O:
C fraction of the pod and seed. The results have demonstrated
that the seed and pod are good bioenergy candidates and the
thermochemical conversion unit can be constructed from the
generated data.

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