Hindawi

Advances in Materials Science and Engineering

Volume 2020, Article ID 7825024, 11 pages
https://doi.org/10.1155/2020/7825024

Research Article
Fast Rate Production of Biodiesel from Neem Seed Oil Using a
Catalyst Made from Banana Peel Ash Loaded with Metal Oxide
(Li-CaO/Fe2 (SO4)3)

Ismail J. Madai,1,2,3 Yusufu Abeid Chande Jande ,1,3 and Thomas Kivevele 1,3

1
Department of Materials and Energy Science and Engineering,
The Nelson Mandela African Institution of Science and Technology, P.O. Box 447, Arusha, Tanzania
2
Department of School Quality Assurance, Ministry of Education, Science and Technology, Dodoma, Tanzania
3
Water Infrastructure and Sustainable Energy Futures (WISE-Futures),
The Nelson Mandela African Institution of Science and Technology, P.O. Box 9124, Nelson Mandela, Arusha, Tanzania

Correspondence should be addressed to Yusufu Abeid Chande Jande; [email protected]

Received 26 April 2020; Accepted 9 July 2020; Published 27 August 2020

Academic Editor: Alicia E. Ares

Copyright © 2020 Ismail J. Madai et al. This is an open access article distributed under the Creative Commons Attribution License,
which permits unrestricted use, distribution, and reproduction in any medium, provided the original work is properly cited.

Biodiesel is a possible remedy to the present toxic, finite sources and ever-diminishing crude fuels. Nonedible and locally available
(Azadirachta indica) neem seed oil (NSO) as a second-generation feedstock was transformed into biodiesel using calcined banana
ash (CBA) derived from banana peels blended with lithium calcium oxide iron (III) sulphate Li-CaO/Fe2 (SO4)3 catalyzed
transesterification. Transesterification process was employed to minimize the free fatty acid (FFA) content of NSO to afford 99.8%
yield under the condition of the reaction oil/methanol ratio 8 : 1, followed by addition of 1.7%wt calcined banana peels ash and
1.3%wt Li-CaO/Fe2(SO4)3 catalysts in 53 min, a notable time. It is important to note that the physicochemical properties of
biodiesel in this study such as initial boiling points, flash point, pour point, cloud point, density, kinematic viscosity, final boiling
points, and cetane index met ASTM D-6751 and EN 14214 standards. Decomposition profile of CBA was displayed by thermal
gravimetric analysis (TGA), whereas in-depth analysis by scanning electron microscope (SEM), X-ray diffraction (XRD), X-ray
fluorescence (X-RF), and Fourier-transform infrared spectroscopy (FT-IR) revealed that the high efficiency displayed by a catalyst
from banana ash calcined at 650°C was due to the presence of potassium carbonate (K2CO3), a calcium magnesium silicate
(CaMgSiO4), and potassium sodium sulphate (KNaSO4) contents that accounted for the high basicity of up to 11.09. Additionally,
the nitrogen adsorption/desorption studies revealed that CBA interestingly exhibits a high BET surface area of 411.2 m2/g and
promising mesopores (3.014 nm). The catalyst also displayed better recyclability evidenced by the fact that it was able to be reused
after five successive runs with better recyclability of 75%. Based on the aforementioned properties, this work, therefore, opens an
avenue for developing a supreme heterogeneous catalyst from available banana peels ash.

1. Introduction problems such as incomplete combustion, high carbon

deposit on the combustion chamber, valve seat, and injector
The current rate of depletion of fossil fuels accompanied by nozzle, therefore, biodiesel is a better option to curb these
environmental pollution justifies the need for scientists to problems as shown by Ahmad et al. [2]. Transesterification is
divert their attention to green and environmentally com- the main method that has been used in the production of
patible energy sources. As one of the most targeted sources biodiesel as shown by Meher et al. [3]. It is a reaction be-
of energy, biodiesel has shown its supremacy by its ability to tween oil and alcohol (methanol/ethanol) giving out com-
undergo degradation and it is also a renewable, affordable, pounds known as alkyl-esters (methyl/ethyl) accompanied
and environmentally friendly source of energy [1]. Having by glycerol as a waste product as shown by Ghadge and
been reported that direct use of plant oil can cause engine Raheman [4]. The intact reaction minimizes parameters
2 Advances in Materials Science and Engineering

such as density, molecular weight, and viscosity and even of the catalyst as well as catalyst reusability. These make the
draws its volatility close to that of diesel fuel by Coniglio catalyst to be more efficient and stand for an environ-
et al. [5]. mentally compatible catalyst for hastening biodiesel pro-
For instance, oil from rapeseed (Ramos et al. [6]), soya duction as a possible substitute fuel raw material.
beans (Gui et al. [7]), sunflower (Antolın [8]), and palm
(Crabbe et al. [9]) has gained attention. Unfortunately, the
use of edible oils poses a risk in food security and therefore,
2. Materials and Methods
the current research trends are targeting nonedible oils as the 2.1. Materials. The ripe banana peels were sourced from the
second generation of biodiesel feedstock (Barnwal and Tengeru market in Arusha, Tanzania. The reagents used were
Sharma [10]). Various nonedible seeds including neem seed, methanol (CH3OH) 99.8%, ethanol (C2H5OH) absolute,
jatropha, croton, and castor beans have been studied and iron (III) sulphate (Fe2(SO4)3), lithium metal (Li), calcium
show good performance in biodiesel production (Atabani oxide (CaO), phenolphthalein (POP) indicator, hydro-
et al. [11]). Neem seeds are derived from unique neem trees chloric acid (HCl) 37%, and Wijis and iodine solution. All
that have a long lifespan estimated to lie between 150 and chemicals were supplied by Sigma-Aldrich and were used
200 years (Schmutterer [12]). It can bear fruits within 3 to 5 without further modification.
years and attains maximum productivity after 10 years and
its oil content varies from 30 to 35% and from 35 to 40% for
kernels and seeds, respectively (Kaura et al. [13]). These 2.2. Preparation of CBA. Ripe banana peels were sliced into
properties necessitate thinking of it as a suitable feedstock small pieces to accelerate the drying process. After washing
for biodiesel production. It is given that 7 to 8 kg of neem with distilled water, banana peels were sundried for 7 days
seed produces one litre of oil. It is also worth mentioning in (turned from yellow to black colour; became light in weight,
this work that planting of neem trees will address not only hard, and wrinkled) followed by oven-drying at 100°C for
energy challenges but also environmental challenges (Kumar 6 h. Then, the dried banana peels were ashed in a box muffle
and Navaratnam [14]). furnace in the presence of air and finally milled and sieved to
Various researches including but not limited to banana a fine powder. The resulting fine ash was annealed in varying
peels as biomass precursors for biodiesel production have temperatures at 100°C interval from 550 to 1050°C for 3 h to
been conducted. For instance, Betiku et al. [15] researched remove impurities [16]. Finally, the calcined ripe banana
on Napoleon’s plumule oil using banana (species Musa gros peel ash was ground and kept in a seal for further analysis.
michel) peels CBA calcined at 700°C for 4 hours with
58.812% potassium composition and Fe2(SO4)3 as a catalyst;
the efficiency for biodiesel yield was 98.05% for 69-minute 2.3. Preparation of Heterogeneous Catalyst. Calcined banana
reaction time with 2 wt% catalyst dosage. Similarly, Gohain ash was tested for basicity by dissolving 5 g of CBA/Li-CaO/
et al. [16] used CBA from banana (species Musa paradisi- Fe2(SO4)3 blends in 50 mL of distilled water using pH meter.
acal) plantain peel from West Africa calcined at 700°C for 4 The blended catalyst metal oxide Li-CaO/Fe2(SO4)3/CBA
hours with 51.02% potassium composition as a catalyst was prepared using 1.3 wt% of lithium calcium oxide (Li-
alongside waste cooking oil and produced 96.3% of biodiesel CaO)/iron (III), sulphate (Fe2(SO4)3), and 1.7 wt% of CB
for 60-minute reaction time with 7.6 wt% catalyst dosage. [1]. Then, 80 mL of methanol was measured using a
The previous application of banana peels as a catalyst for measuring cylinder and poured in a conical flask. The
biodiesel production tends to be a slow, time-consuming, blended catalyst was dissolved in methanol with contin-
large dosage of catalyst usage and large waste disposal. This is uous stirring of 2700 rpm within 5 min. Then, the solution
due to low potassium content as well as low basic strength of the blended catalyst was ready and finally waited for
which resulted from high calcined of CBA at 700°C which is further activity.
close to the melting point (740°C) of potassium oxide
[15, 16]. This calcination may lead to the reaction to take
longer time and hence a large dosage of catalyst usage and 2.4. Characterization of the Heterogeneous Catalyst.
large waste production. The efficiency of basic contents Micrometrics instruments (ASP2020) were employed for
determines the time for the production of biodiesel. nitrogen sorption studies. Functional groups in the sample
The common species of banana with high availability in such as calcined banana ash were analyzed by using Fourier-
Arusha Tanzania as well as East Africa is Musa acuminata transform infrared (FT-IR) instrument. The model of FT-IR
Colla. These banana species are used as food but their peels used in this study was Alpha Bruker ATR, the wavenumber
are treated as wastes [17, 18]. These peels have high po- ranging from 4000 to 1000 cm−1, and XRF for elemental
tassium contents which can be used as a biocatalyst for analysis composition. Thermogravimetric analysis was used
biofuel production [19]. However, using these peels will to show the decomposition profile of the sample. Approx-
increase banana production as well as solving the energy imately, 0.24 mg of the sample was subjected to a temper-
problem. ature range from 29°C to 800°C in a time interval of 5.38 to
On top of that, this leads to come up with loading metal 78.48 min. TGA gives a clear indication that the calcined
oxide Li-CaO/Fe2 (SO4)3 to CBA biocatalyst which forms a temperature should start at 650°C. Finally, the ground
strong basic catalyst that increases the oxidation by con- catalyst precursor was subjected to heat treatment in a box
verting free fatty acid to methyl esters and the performance furnace for 3 h at 650°C.
Advances in Materials Science and Engineering 3

2.5. Neem Seed Oil Preparation. Neem seeds were purchased were determined by test cabinet instruments, PSL System-
from Bagamoyo, Iringa, and Singida regions in Tanzania. technik/product/pour point tester 45150 and ASTM D2500
Initially, the seeds were washed with distilled water and then cloud point testing. The flashpoint was determined with the
sundried for five days to remove moisture content, whereas aid of Pensky-Martens flash point tester, PMA 5, Anton-
other solid dirty impurities were removed by handpicking Paar.com instruments as per ASTM D93 standards. The
and winnowing processes [20]. Seeds were soaked in water approximation of various values of acid, iodine, and sa-
for 24 h to remove husks and finally pressed using a hy- ponification was done through the titration method.
draulic pressing machine to obtain the oil.
2.8. Recyclability of the Catalyst. Heterogeneous catalysts
2.6. Biodiesel Production through Transesterification Process. have gained fame as compared to homogeneous catalysts
Transesterification process of NSO to biodiesel (methyl because of their reusability [26]. Therefore, the recyclability
esters) was carried out using 1.7 wt% of CBA loaded with Li- of the catalyst synthesized in this study was determined as
CaO/Fe2 (SO4)3, 100 mL methanol, and 800 mL of NSO. The follows. Methanol was used to wash the catalyst spent in the
blended catalyst (1.7 wt% CBA/Li-CaO/Fe2 (SO4)3) was biodiesel production to remove the contents of glycerol and
mixed with 100 mL of methanol with continuous stirring at oil. Since water is a product of the transesterification process,
2700 rpm for five minutes, which was finally followed by the catalyst was later oven-dried for 2 h at a temperature of
addition into 800 mL of NSO (warmed to 40°C) with con- 110°C. After drying and cooling, the spent catalyst was
tinuous stirring until two immiscible layers of biodiesel (top successfully used to produce biodiesel for the next successive
layer) and glycerol (bottom layer) were formed. This reac- run. Biodiesel yield produced was calculated after every
tion was performed in 2000 mL conical flask and took successful run till the fifth run.
53 min. The conical flask was covered with aluminium foil
and temperature was monitored by a thermometer under a 3. Results and Discussions
constant temperature of 60°C; above this temperature,
methanol will be boiled which will reduce the production of 3.1. Characterization of the Catalyst
biodiesel [21]. The experiment was carried in a water bath
3.1.1. Thermogravimetric Analysis (TGA). Figure 1 shows
until two immiscible layers of biodiesel (top layer) and
the TGA graph with plateaus at 650°C, a clear indication that
glycerol (bottom layer) were formed [22]. This trans-
all the impurities have been lost and mostly only the metal
esterification reaction takes place in alcoholic condition
oxides such as CaO, K2CO3 MgO, and Na2O remained
(methanol) as the media for the reaction to take place in
which increase the performance of the catalyst [27]. Above
presence of catalyst which speeds up the reaction but re-
740°C, most of the metal oxides like potassium were
mains unchanged at the end of the reaction [23]. Both
decomposed which decrease the basicity and, thus, decrease
separating funnel and filtration methods were employed to
catalyst performance [28].
isolate the catalyst from the reaction mixture and finally, the
filtrate was washed and dried with anhydrous sodium sul-
phate [24]. The process was repeated using the same filtrate 3.1.2. Textural Properties. For structural identification of
catalyst up to the fifth run. The transesterification process CBA loaded with Li-CaO/Fe2(SO4)3 which was character-
was repeated by varying catalyst dosage from 1 to 1.7 wt% ized, the BET method was used to determine the surface area,
and methanol-to-oil molar ratio varies from 2 : 1 to 16. while Barret-Joyner Halenda (BJH) method was used to
Finally, biodiesel produced was tested using phenolphtha- determine pore sizes and pore volume. CBA Li-CaO/
lein indicator where the colour changes from clear to pink at Fe2(SO4)3 blends possess a BET surface of 411 m2/g, pore
a pH of 8-9 and the universal indicator was also used where diameter of 3.0 nm, and pore volume of 0.628 cm3/g.
the colour changes from green to dark green at pH of 8-9. According to previous studies on BET and BJH method in
However, the percentage of biodiesel yield was calculated by structural identification, CBA possesses a BETsurface of 4 m2/
weighing the mass of biodiesel produced over the mass of oil g, pore diameter of 18 nm, and pore volume of 0.02 cm3/g
used times hundred [25]. This was calculated using (Betiku et al. [15]). According to Gohain et al. [16], CBA
possesses a BET surface of 14 m2/g, pore diameter of 0.6 nm,
weight of biodiesel obtained and pore volume of 0.065 cm3/g. The CBA Li-CaO/Fe2(SO4)3
percentage biodiesel yield � × 100.
weight of oil used complex shows the large surface area as urged with results
(1) obtained by Zabeti et al. [29]. The CBA/Li-CaO/Fe2(SO4)3
contributed to an increase in performance and reusability of
the catalyst due to its high basic contents with a pH of 11.1.
This implies that specific surface area, as well as the pore
2.7. Characterization of Biodiesel Properties. Fatty acid
volume, reusability, and high basic strength, may have a
composition analysis for NSO was done using Gas Chro-
significant contribution to the performance of the catalyst.
matography-Mass Spectrometry (GC-MS), Anton Paar
Stabinger viscometer SVM 4001, and density meter DMI
5000. Anton Paar.com instruments were used to determine 3.1.3. FT-IR Spectra Analysis. FT-IR spectra of banana ashes
kinematic viscosity at 40°C and density of biodiesel at 15.5°C loaded with metal oxide Li-CaO/Fe2(SO4)3 were charac-
per ASTM D7042 standards. Pour point and cloud point terized as illustrated in Figures 2(a)–2(c) and compared to
4 Advances in Materials Science and Engineering

Burning time (min)

0 10 20 30 40 50 60 70 80
1

–1

Weight loss (mg)

–2

–3

–4

–5

0 100 200 300 400 500 600 700 800

Temperature (°C)
Figure 1: Decomposition profile of catalyst between 29 and 800°.

1.040
Transmittance (%)
Transmittance (%)

0.986 0.975
512
0.957 3303 0.910 681
1016 2920
0.928 1362 1603
2920 0.845
1027 1351
0.899 0.780
1000 2000 3000 4000 1000 2000 3000 4000
–1)
Wavenumber (cm–1) Wavenumber (cm
(a) (b)

0.979
Transmittance (%)

452
0.890 3148
692
884
0.801

0.712 1376
1000 2000 3000 4000
Wavenumber (cm–1)
(c)

Figure 2: FT-IR peaks of banana ashes blends: (a) fresh banana ash blends, (b) burnt banana ash blends, and (c) calcined banana as blends.

each other. The broadband at 3303 cm−1 in Figure 2(a) shows worth mentioning that a well-pronounced peak of K2CO3
the stretching vibration of the O-H group and in located at 1376 cm−1 is of special interest given that K2CO3
Figures 2(b) and 2(c), the O-H group disappeared due to comes with several advantages such as increased catalyst
burning in air and calcination at 650°C. The sharp peak and performance, surface area, and reusability and prevents
small peak observed at 2920 cm−1 in Figure 2(a) and leaching as reported elsewhere [15].
2900–3150 cm−1 in Figures 2(b) and 2(c), respectively, show
the stretching vibration of the C-H. Bands observed at
1350–1380 cm−1 have been associated with stretching vi- 3.1.4. Morphological Analysis. A scanning electron micro-
brations of C-O from carbonate which show similarity with scope displays images at a magnification of 5000× resolution.
wavenumber [30]. The bending vibrations observed at The micrographs are shown in Figures 3(a)–3(c) which
500–1020 cm−1 show some elements of interest since the represent fresh banana ash blends, burnt banana ash blends,
peaks are associated with CaMgSiO4, Li2O, and FeSO4. It is and calcined banana ash blends. The surface of Figure 3(a)
Advances in Materials Science and Engineering 5

(a) (b) (c)

Figure 3: SEM images of (a) fresh banana ash blends, (b) burnt banana ash blends, and (c) calcined banana ash blends.

shows a smooth and flat nature of fresh banana ash blends, was reasonably high, suggesting that there was a high level of
while Figure 3(b) has a mixture of small flake-like aggregates, free fatty acid contents that probably would result in soap
and lastly Figure 3(c) displays interestingly sponge-like formation [11]. For oils with FFA contents higher than 1.1%,
microstructure, a clear indicator of increased surface area it is desirable to apply a biomass catalyst to maximize the
which is proportional to the activity of the catalyst. This is in yield of biodiesel production as this may prevent the reaction
line with the argument of Sharma and his group who ob- that results in soap formation [33]. The physicochemical
served that heat treatment hinders leaching of K and, identification of NSO like acid value and saponification
therefore, increases the life of the catalyst [31]. value as well as iodine value was done through titration
process in line with the agreements of American Society for
Testing and Materials (ASTM) in the year 1983 and rec-
3.1.5. XRD Analysis. For crystallographic identification,
ommended the practice of official methods of American Oil
XRD analysis was carried out on calcined banana ash (CBA)
Chemists Society (AOCS) [34].
blends, burnt banana ash (BBA) blends, and fresh banana
The weight of oil extracted from a given mass in grams of
ash (FBA) blends as shown in Figures 4(a)–4(c). There was a
seed pressed was measured to determine the lipid contents.
significant increase in potassium compounds with an in-
The results were expressed as the percentage of oil in the dry
crease in calcination temperature up to 650°C as shown in
matter [35]:
Figure 3(a). Sharp pronounced peaks at 2θ : 29 degrees
correspond to K2CO3, whereas peaks at 2θ : 33 and 43 de- percentage of oil in sample
grees correspond to CaMgSiO4 and KNaSO4, respectively.
Remarkable crystallinity of the materials can be observed weight of dry seed − weight of residue (2)
from the fact that the peaks are narrow with high intensity. � .
weight of seed after dry
Additionally, weak unmarked peaks in Figures 3(a)–3(c)
may be attributed to trace elements like Fe2(SO4)3 and Li2O The acid value (AV) of neem oil was determined by
which have been reported to have a significant contribution titration method, diethyl ether, ethanol (95%), and phe-
to basicity and consequently optimize the catalyst perfor- nolphthalein indicator, and a given mass oil sample in the
mance (Betiku et al. [32]). mixture was titrated with 0.1 M NaOH in triplicate of ex-
periments. The AV was calculated using the following
equation [36]:
3.1.6. Elemental Composition of CBA. Table 1 shows that the
results of the XRF analysis carried on banana ashes calcined acid value
at different temperatures ranged from 550 to 1050°C and
finally loaded with Li-CaO/Fe2(SO4)3. These results show the titre volume × grams of NaOH in 0.1 M of NaOH solution
� .
elemental composition present in banana ash. Main ele- sample weight in grams
ments present in banana ash complex after sample analysis (3)
were K, Na, Ca, Mg, Fe, Al, Si, S, Li, and Cl. Potassium is the
element of interest which has shown highest percentage Iodine value (IV) is the measure of the degree of
(74.4%) composition after calcination at 650°C; the ash unsaturation of an oil or fat. Determination of IV in neem
produced at 650°C was used as a catalyst for rapid pro- seed oil was carried out using laboratory titration method
duction of biodiesel. where a given mass of dry soil sample was mixed with a given
2.2. Physicochemical Properties of NSO volume of carbon tetrachloride, Wijis reagent 10%, potas-
The physicochemical results were shown in Table 2. The sium iodide solution, and distilled water to make a solution
amount of oil in one kilogram of neem seeds was 37.28% and titrate with 0.1 N of (Na2S2O3) sodium thiosulphate
which was enough for the high production of biodiesel. solution. The iodine value for the oil in the solution is
From the following results, the concentration of acid value calculated using the following equation [21]:
6 Advances in Materials Science and Engineering

Δ ∆
Intensity counts

Intensity counts
□ Ο Ο
□

10 20 30 40 50 60 70 80 90 10 20 30 40 50 60 70 80 90
2-theta (deg) 2-theta (deg)

Δ K2CO3 Δ K2CO3
□ CaMgSiO4 □ CaMgSiO4
Ο KNaSO4 Ο KNaSO4
(a) (b)
Intensity counts

∆
Ο

10 20 30 40 50 60 70 80 90
2-theta (deg)

Δ K2CO3
Ο KNaSO4
(c)

Figure 4: XRD pattern of (a) calcined banana ash blends, (b) burnt banana ash blends, and (c) fresh banana ash blends.

Table 1: Elemental composition of CBA blends.

Temp (°C) K Cl Si (wt.%) Na S Li Al Mg Ca Fe
550 54.65 7.37 4.955 3.21 3.15 1.84 1.49 1.42 1.27 0.14
650 74.41 10.88 5.22 2.88 0.00 2.96 0.21 1.19 1.62 0.25
750 72.51 11.36 5.79 3.79 0.00 3.02 0.18 0.70 1.68 0.28
850 72.34 7.0 9.53 3.86 0.00 2.94 1.51 0.41 1.21 0.35
950 63.08 3.19 20.34 3.33 0.057 2.27 1.88 1.40 2.39 0.83
1050 67.06 0.92 16.15 4.49 0.39 3.17 1.11 1.55 3.22 0.64

Table 2: Physicochemical properties of NSO. indicator was added to the sample and then titrated with 0.5
Property Unit NSO MHCl. The saponification value was calculated using the
following equation [37]:
Oil content % 37.28
Acid value mgKOH/g 0.46 (b − a) × grams of KOH in 0.5 M KOH solution
Iodine value gI2/100 g 81.06 S.V � ,
sample weight in grams
Saponification value mgKOH/g 134.8
Free fatty acid (FFA) mgKOH/g 0.23 (5)
where a indicates volume of oil solution and b indicates
volume of titre of the blank solution [38]. One has
(b − a) × mass of iodine in 0.1 N of sodium thiosulphate
I.V � , acid value
sample weight in grams free fat acid � . (6)
(4) 2

where a and b are average titration volumes (ml) of blank

and oil solution and N is the normality of sodium 3.1.7. Fatty Acid Profile of Neem Oil. Table 3 shows that
thiosulphate. neem oil was extremely unsaturated (67.62%) due to the
The saponification value (SV) of neem seed oil was availability of linoleic acid, pentadecanoic acid, oleic acid,
determined by titrating a given mass of oil dissolved in a and linolenic acid as the major methyl esters. Literature
given volume of ethanolic potassium hydroxide (0.5 M in reports that methyl esters from neem oil are extremely
95% ethanol) heated for one hour and then phenolphthalein unsaturated [39].
Advances in Materials Science and Engineering 7

3.2. Characterization of Biodiesel. The properties of biodiesel of oil at an interval of 0.1 wt% from 1 to 2 wt%. The effect of
produced from blends of CBA/Li-CaO/Fe2 (SO4)3 are catalyst loaded on the rate of production of biodiesel yield
summarized in Table 4. Interestingly, these properties show was increased from 1.1 to 1.7 wt%, respectively, whereby the
similarities with the standards specified in EN 14214 and percentage of conversion of biodiesel was increased. The
ASTM D 6751. For instance, the close similarity in cloud highest production yields 98.8% of biodiesel were attained at
pour points, viscosity, initial boiling points, final boiling catalyst to oil weight of 1.7 wt% as shown in Figure 5. Several
points, and acid value was observed. With an exception of factors might have contributed to the high production yield
density which was slightly higher than the recommended of biodiesel, for example, the high surface area of the catalyst
range, all other properties were per the ASTM D6751 and presence of basic metal oxides such as K, Na, Ca, and
standards. However, this biodiesel produced displayed re- Mg, which contributed to high basic strength 11.1 of the
markable cold flow properties like cloud point, pour point, catalyst. Also, the availability of higher oxygen compounds
and kinematic viscosity and may be used in cold areas. Also, in Li-CaO/Fe2(SO4)3 increases the rate of conversion methyl
the calorific value was high. It has been reported in the ester to biodiesel [42, 43].
literature that both the molecular mass of methyl ester and
its saturation level determine the density of biofuel; in
short, the unsaturation level is directly proportional to the 3.3.2. Effect of Reaction Time. Production of biodiesel in-
specific gravity [40]. The high density of biodiesel from creases with the increase of time of the reaction [44]. The
neem oil may be due to the high unsaturation level. It is conversion rate of biodiesel depends on the time response
important to note that partial combustion has been re- for the required chemical reaction to take place [45]. The
ported because of the poor atomization process from the production biodiesel using NSO with 1.7 wt% catalyst
fact that denser fuels are less compressible [11]. Flashpoint loading and 8 : 1 excess methanol was done by changing the
as one of the most important parameters in the diesel time of the reaction after every 10 min from 10 to 70 min
engine can be defined as a minimum temperature at which while stirring at 2700 rpm and maintaining the temperature
fuel ignites [20]. In this study, it was about 150 °C. This at 60°C. Figure 6 shows the effects of time on biodiesel yield.
temperature not only meets the required ASTM D6751 It is observed that the rate of production of biodiesel yield
standards, which recommends a minimum of 130 °C, but increases with time from 10 min to around 50 min. Above
also guarantees safety especially during storage and 50 min, biodiesel yield remained constant. This is due to a
transportation [41]. The produced biodiesel and catalyst reversible reaction caused by the reduced and disappearance
from this study show high yield compared to other studies of esters resulting in soap formation associated with the fatty
as reported in Table 4. acid composition [46]. It observed that the proper time for
Table 5 shows several precursors including but not the production of the highest yield of biodiesel is 53 min.
limited to banana peels that have been investigated as
biomass precursors for biodiesel production. For instance, 3.3.3. The Effect of Methanol-to-Oil Ratio. Key factors for
Betiku et al. [15] researched on banana peel using Napo- converting long fatty acid esters to methyl esters (biodiesel)
leon’s plumule oil and produced biodiesel 98.5% for 69- are the ratio of methanol to oil. The relation between
minute reaction time. In a similar study conducted by quantities of substance and the number of moles that can
Gohain et al. [16], banana peel as a catalyst was used take part in a chemical reaction is needed in the process [33].
alongside waste cooking oil and it produces a biodiesel This can result in the split of the mixture of reaction on the
96.3% for 60-minute reaction time. This study now reveals solubility of glycerol to the methyl ester layer. Figure 7 shows
that CBA/Li-CaO/Fe2 (SO4)3 blended catalyst is anticipated that the best ratio that can be seen as methanol-to-oil ratio of
to reduce the reaction time in the production of biodiesel 8 : 1 highest yield of biodiesel was attained. This intensifies
98.8% for 53-minute reaction time. Therefore, the blended the equilibrium reaction which may affect the production
catalyst is economical for the production of biodiesel from biodiesel yield [46].
NSO as a possible alternative fuel feedstock in biodiesel
production.
3.4. Catalyst Recyclability. Bio-based catalyst precursor
prepared was reused up to the fifth run in the trans-
3.3. Performance of Catalyst for Biodiesel Production esterification process, under the optimum condition, 1.7 wt
% catalyst feed, methanol-to-oil molar ratio 8 : 1, 53 min time
3.3.1. The Effect of Catalyst Loading. The production of of the reaction, 60°C temperatures of the reaction, and
biodiesel yield was done by evaluating the percentage per- stirring rate of 2700 rpm. From Figure 8, one can see that
formance of the CBA blended catalyst using (1), by changing catalyst performance in biodiesel yield decreased in every
the conditions of the parameters of the reaction like per- successive route. The yield was as follows: 98.8, 96.7, 85.7,
centage by weight of the catalyst added, the reaction time- 82.8, and 75.6% in the first, second, third, fourth, and fifth
temperature set, and the ratio of methanol and neem oil run, respectively. This may be due to the loss of functional
used. The amount of produced biodiesel was affected by the groups of the catalyst. The loss of the catalyst active site may
amount of the catalyst. The excess ratio of 16 : 1 of methanol be due to H2O and CO2 from the environments. Recycla-
to oil was used during testing the performance of the cat- bility of the catalyst numerously shows the great significance
alyst. The amount of catalyst added varied with the amount of the bio-based catalyst in minimizing waste disposal and
8 Advances in Materials Science and Engineering

Table 3: Fatty acid composition of neem oil.

Fatty acid Formula Systematic name Structure wt.(%)
Saturated fatty acids
Palmitic C16H32O2 Hexadecanoic acid 16 : 0 10.92
Stearic C18H36O2 (E)-9-Octadecenoic acid 18 : 1 19.85
Arachidic C20H40O2 Eicosanoic acid 20.0 1.35
Lignoceric C24H48O2 Tetracosanoic acid 24.0 0.26
Total 32.38
Unsaturated fatty acids
Pentadecanoic C17H34O2 Pentadecanoic acid, 14 17 : 1 2.57
Oleic C18H34O2 9-Octadecenoic acid 18 : 1 1.82
Linoleic C18H32O2: 9,12-Octadecadienoic acid 18 : 1 52.51
Linolenic C18H30O2 9,12-Octadecatrienoic acid 18 : 1 10.71
Total 67.62

Table 4: Physicochemical properties of neem biodiesel.

Test/characteristics Petrol diesel ASTM D975 limits Biodiesel ASTM D 6751 limits Biodiesel
Density at 15 kg/m3 850 860–900 863.8
Kinematics viscosity at 40°C (mm2/s) 2–4.5 1.9–6.0 3.8
Pour point (°C) −35 to −15 NS −30
Flashpoint (°C) 60–80 130 min 150
Cloud point (°C) −15 to −5 NS −40
Cetane index (minimum) — 47 48.9
Initial boiling point (°C) — NS 86
Final boiling point (°C) — NS 86
Calorific value 42–46 — 43
Acid value (titration) (mgKOH/g) — 0.5 max 0.12

Table 5: Comparison of the different performance of catalyst for biodiesel production.

Heterogeneous Surface area Catalyst dosage Alcohol/oil Temp Time Yield
Feedstock Reference
catalyst type (m2/g) (wt.%) ratio (°C) (min) (wt.%)
Napoleon’s
Banana peels 4.44 2.75 30 : 1 65 69.02 98.50 [15]
plumule oil
Banana peels Waste cooking oil 14.036 2 9 :1 60 80 96.3 [16]
CBA Neem seed oil 411.2 1.7 8.1 60 53 98.80 This study

100

95
Biodiesel yield (%)

90

85

80

75

70

1.0 1.2 1.4 1.6 1.8 2.0

Catalyst loading (wt%)
Figure 5: Effect of the amount of catalyst added on the production of biodiesel.
Advances in Materials Science and Engineering 9

production expenses and is environmentally friendly during

100 the production of biodiesel.

4. Conclusion
Biodiesel yield (%)

This study presents the production of biodiesel from NSO

80 and affordable solid catalyst synthesized by direct calcina-
tion of banana peels. Calcined banana peels at 650°C ac-
quired good catalytic activity due to the presence of basic
metal oxides of K, Ca, Na, and Mg and basic strength of
11.09. The performance was also attributed to its high
60
specific surface area of 411 m2/g and pore diameter of
3.0 nm. The maximum biodiesel production yield of 98.8%
was achieved at a low catalyst loading of 1.7 wt% and 8 : 1
10 20 30 40 50 60 70 methanol-to-oil molar ratio at a temperature of 60°C. The
Reaction time (min) produced biodiesel acquired physicochemical parameters
Figure 6: Effect of reaction time on biodiesel yield. within the recommended ASTM D6751 standards and it
displayed remarkable cold flow properties, that is, cloud
point, pour point, and kinematic viscosity, and may be used
in cold areas; also the calorific value was high. The catalyst
100 shows good reusability properties with a yield of approxi-
mately 75% after a fifth run. It can be concluded that the
98 produced CBA catalyst minimizes waste disposal, hence
standing out as an environmentally compatible catalyst.
96
Biodiesel yield (%)

94
Data Availability
The data used to support the findings of this study are
92
available from the corresponding author upon request.
90
Conflicts of Interest
88
The authors declare that there are no conflicts of interest in
86 this work.
2: 1 4 :1 6 :1 8 :1 10:1 12: 1 14:1 16 :1
Methanol : oil Authors’ Contributions
Figure 7: Effect of the ratio of methanol and oil on a yield of All the authors have approved the manuscript.
biodiesel.
Acknowledgments
The authors acknowledge the financial support from Water
Infrastructure and Sustainable Energy Futures (WISE-Fu-
100
tures) and other supports from the Nelson Mandela African
Institution of Science and Technology (NM-AIST) and The
80 World Academy of Science (TWAS).
Biodiesel yield (%)

60 Supplementary Materials
40 Figure S1 shows procedures for preparation of calcined
banana ash (CBA) catalyst. This was done by slicing the
banana peel followed by sun drying then oven drying and
20
finally calcination at 650°C to obtain the required catalyst.
Figure S2 shows procedures for extraction of oil from neem
0
seed. Neem seed oil was extracted using a hydraulic pressing
machine. Neem seeds were fed to the machine and then
0 5 10 pressed to produce oil. Figure S3 shows biodiesel production
Number of runs steps through transesterification process using CBA loaded
Figure 8: The recyclability catalyst versus % of biodiesel with metal oxide (Li-CaO/Fe2 (SO4)3 as a catalyst. (Sup-
production. plementary Materials)
10 Advances in Materials Science and Engineering

References biodiesel production,” Industrial Crops and Products, vol. 109,

pp. 8–18, 2017.
[1] A. K. Endalew and Y. Kiros, “Catalytic autoxidation of fatty [17] P. Onwuachi-Iheagwara, “Comparative analysis of the use of
acid methyl esters from jatropha oil,” Journal of Fuels, banana peels and NaOH in Ph control in Nigerian clays,”
vol. 2014, Article ID 470790, 6 pages, 2014. Journal of the Nigerian Association of Mathematical Physics,
[2] A. L. Ahmad, N. H. M. Yasin, C. J. C. Derek, and J. K. Lim, vol. 30, pp. 197–202, 2015.
“Microalgae as a sustainable energy source for biodiesel [18] E. G. N. Mbanjo, F. Tchoumbougnang, A. S. Mouelle et al.,
production: a review,” Renewable and Sustainable Energy “Molecular marker-based genetic linkage map of a diploid
Reviews, vol. 15, no. 1, pp. 584–593, 2011. banana population (Musa acuminata colla),” Euphytica,
[3] L. C. Meher, D. V. Sagar, and S. Naik, “Technical aspects of vol. 188, no. 3, pp. 369–386, 2012.
biodiesel production by transesterification—a review,” Re- [19] A. M. Khan, S. Khaliq, and R. Sadiq, “Investigation of waste
newable and Sustainable Energy Reviews, vol. 10, no. 3, banana peels and radish leaves for their biofuels potential,”
pp. 248–268, 2006. Bulletin of the Chemical Society of Ethiopia, vol. 29, no. 2,
[4] S. V. Ghadge and H. Raheman, “Process optimization for pp. 239–245, 2015.
biodiesel production from mahua (Madhuca indica) oil using [20] N. Z. Dimetry, S. Amer, and A. S. Amer, “Biological activity of
response surface methodology,” Bioresource Technology, two neem seed kernel extracts against the two-spotted spider
vol. 97, no. 3, pp. 379–384, 2006. mite Tetranychus urticae Koch,” Journal of Applied Ento-
[5] L. Coniglio, H. Bennadji, P. A. Glaude, O. Herbinet, and mology, vol. 116, no. 1–5, pp. 308–312, 1993.
F. Billaud, “Combustion chemical kinetics of biodiesel and [21] N. B. Kyriakidis and T. Katsiloulis, “Calculation of iodine
related compounds (methyl and ethyl esters): experiments value from measurements of fatty acid methyl esters of some
and modeling-advances and future refinements,” Progress in oils: comparison with the relevant American oil chemists
Energy and Combustion Science, vol. 39, no. 4, pp. 340–382, society method,” Journal of the American Oil Chemists’ So-
2013. ciety, vol. 77, no. 12, pp. 1235–1238, 2000.
[6] M. J. Ramos, C. M. Fernández, A. Casas, L. Rodrı́guez, and [22] Y. A. Elsheikh, “Preparation of Citrullus colocynthis bio-
Á. Pérez, “Influence of fatty acid composition of raw materials diesel via dual-step catalyzed process using functionalized
on biodiesel properties,” Bioresource Technology, vol. 100, imidazolium and pyrazolium ionic liquids for esterification
no. 1, pp. 261–268, 2009. step,” Industrial Crops and Products, vol. 49, pp. 822–829,
[7] M. M. Gui, K. T. Lee, and S. Bhatia, “Feasibility of edible oil vs. 2013.
non-edible oil vs. waste edible oil as biodiesel feedstock,” [23] A. Abbaszaadeh, “Current biodiesel production technologies:
Energy, vol. 33, no. 11, pp. 1646–1653, 2008. a comparative review,” Energy Conversion and Management,
[8] G. Antolın, “Optimisation of biodiesel production by sun- vol. 63, pp. 138–148, 2012.
flower oil transesterification,” Bioresource Technology, vol. 83, [24] M. Xiao, S. Mathew, and J. P. Obbard, “Biodiesel fuel pro-
no. 2, pp. 111–114, 2002. duction via transesterification of oils using lipase biocatalyst,”
[9] E. Crabbe, C. Nolasco-Hipolito, G. Kobayashi, K. Sonomoto, Gcb Bioenergy, vol. 1, no. 2, pp. 115–125, 2009.
and A. Ishizaki, “Biodiesel production from crude palm oil [25] M. Elkady, A. Zaatout, and O. Balbaa, “Production of bio-
and evaluation of butanol extraction and fuel properties,” diesel from waste vegetable oil via KM micromixer,” Journal
Process Biochemistry, vol. 37, no. 1, pp. 65–71, 2001. of Chemistry, vol. 2015, Article ID 630168, 9 pages, 2015.
[10] B. K. Barnwal and M. P. Sharma, “Prospects of biodiesel [26] H. Ibrahim, “Advancement in heterogeneous catalysis of
production from vegetable oils in India,” Renewable and triglycerides for biodiesel production,” International Journal
Sustainable Energy Reviews, vol. 9, no. 4, pp. 363–378, 2005. of Engineering and Computer Science, vol. 2, no. 5,
[11] A. E. Atabani, A. S. Silitonga, H. C. Ong et al., “Non-edible pp. 1426–1433, 2013.
vegetable oils: a critical evaluation of oil extraction, fatty acid [27] Z. Zhang, S. Yang, M. Dou, H. Liu, L. Gu, and F. Wang,
compositions, biodiesel production, characteristics, engine “Systematic study of transition-metal (Fe, Co, Ni, Cu)
performance and emissions production,” Renewable and phthalocyanines as electrocatalysts for oxygen reduction and
Sustainable Energy Reviews, vol. 18, pp. 211–245, 2013. their evaluation by DFT,” RSC Advances, vol. 6, no. 71,
[12] H. Schmutterer, “Properties and potential of natural pesti- pp. 67049–67056, 2016.
cides from the neem tree, Azadirachta indica,” Annual Review [28] N. Iwamoto, “Melting points of inorganic fluorides,” Trans-
of Entomology, vol. 35, no. 1, pp. 271–297, 1990. actions of JWRI, vol. 2, no. 2, pp. 204–207, 1973.
[13] S. K. Kaura, S. K. Gupta, and J. B. Chowdhury, “Morpho- [29] M. Zabeti, W. M. A. W. Daud, and M. K. Aroua, “Activity of
logical and oil content variation in seeds of Azadirachta indica solid catalysts for biodiesel production: a review,” Fuel Pro-
A. Juss. (neem) from northern and western provenances of cessing Technology, vol. 90, no. 6, pp. 770–777, 2009.
India,” Plant Foods for Human Nutrition, vol. 52, no. 4, [30] J. R. Memon, S. Q. Memon, M. I. Bhanger, G. Z. Memon,
pp. 293–298, 1998. A. El-Turki, and G. C. Allen, “Characterization of banana peel
[14] V. S. Kumar and V. Navaratnam, “Neem (Azadirachta indica): by scanning electron microscopy and FT-IR spectroscopy and
prehistory to contemporary medicinal uses to humankind,” its use for cadmium removal,” Colloids and Surfaces B: Bio-
Asian Pacific Journal of Tropical Biomedicine, vol. 3, no. 7, interfaces, vol. 66, no. 2, pp. 260–265, 2008.
pp. 505–514, 2013. [31] M. Sharma, A. A. Khan, S. K. Puri, and D. K. Tuli, “Wood ash
[15] E. Betiku, A. M. Akintunde, and T. V. Ojumu, “Banana peels as a potential heterogeneous catalyst for biodiesel synthesis,”
as a biobase catalyst for fatty acid methyl esters production Biomass and Bioenergy, vol. 41, pp. 94–106, 2012.
using Napoleon’s plume (Bauhinia monandra) seed oil: a [32] E. Betiku, A. O. Etim, O. Pereao, and T. V. Ojumu, “Two-step
process parameters optimization study,” Energy, vol. 103, conversion of neem (Azadirachta indica) seed oil into fatty
pp. 797–806, 2016. methyl esters using a heterogeneous biomass-based catalyst:
[16] M. Gohain, A. Devi, and D. Deka, “Musa balbisiana colla peel an example of cocoa pod husk,” Energy & Fuels, vol. 31, no. 6,
as highly effective renewable heterogeneous base catalyst for pp. 6182–6193, 2017.
Advances in Materials Science and Engineering 11

[33] H. J. Berchmans and S. Hirata, “Biodiesel production from

crude Jatropha curcas L. seed oil with a high content of free
fatty acids,” Bioresource Technology, vol. 99, no. 6,
pp. 1716–1721, 2008.
[34] C. Martı́n, A. Moure, G. Martı́n, E. Carrillo, H. Domı́nguez,
and J. C. Parajó, “Fractional characterisation of jatropha,
neem, moringa, trisperma, castor and candlenut seeds as
potential feedstocks for biodiesel production in Cuba,” Bio-
mass and Bioenergy, vol. 34, no. 4, pp. 533–538, 2010.
[35] L. Niu, J. Li, M.-S. Chen, and Z.-F. Xu, “Determination of oil
contents in Sacha inchi (Plukenetia volubilis) seeds at dif-
ferent developmental stages by two methods: soxhlet ex-
traction and time-domain nuclear magnetic resonance,”
Industrial Crops and Products, vol. 56, pp. 187–190, 2014.
[36] F. Kusu, T. Fuse, and K. Takamura, “Voltammetric deter-
mination of acid values of fats and oils,” Journal of AOAC
International, vol. 77, no. 6, pp. 1686–1688, 1994.
[37] S. Dileesh, Determination of Saponification, Acid and Ester
Values; Percentage of Free Fatty Acids and Glycerol in Some
Selected Edible Oils: Calculation of Concentration of Lye
Needed to Prepare Soap from these Oils, Scholars Association
of Kerala, Kottayam, Kerala, 2013.
[38] D. E. Bowyer, W. M. F. Leat, A. N. Howard, and
G. A. Gresham, “The determination of the fatty acid com-
position of serum lipids separated by thin-layer chromatog-
raphy; and a comparison with column chromatography,”
Biochimica et Biophysica Acta, vol. 70, pp. 423–431, 1963.
[39] H. Muthu, V. SathyaSelvabala, T. K. Varathachary,
D. Kirupha Selvaraj, J. Nandagopal, and S. Subramanian,
“Synthesis of biodiesel from neem oil using sulfated zirconia
via tranesterification,” Brazilian Journal of Chemical Engi-
neering, vol. 27, no. 4, pp. 601–608, 2010.
[40] H. Ong et al., “Production and comparative fuel properties of
biodiesel from non-edible oils: jatropha curcas, Sterculia
foetida and Ceiba pentandra,” Energy Conversion and Man-
agement, vol. 73, pp. 245–255, 2013.
[41] J. Blin, C. Brunschwig, A. Chapuis et al., “Characteristics of
vegetable oils for use as fuel in stationary diesel engines-
Towards specifications for a standard in West Africa,” Re-
newable and Sustainable Energy Reviews, vol. 22, pp. 580–597,
2013.
[42] F. Guo, Z.-G. Peng, J.-Y. Dai, and Z.-L. Xiu, “Calcined sodium
silicate as solid base catalyst for biodiesel production,” Fuel
Processing Technology, vol. 91, no. 3, pp. 322–328, 2010.
[43] L. Buchori, I. Istadi, and P. Purwanto, “Advanced chemical
reactor technologies for biodiesel production from vegetable
oils-a review,” Bulletin of Chemical Reaction Engineering &
Catalysis, vol. 11, no. 3, pp. 406–430, 2016.
[44] H. He, T. Wang, and S. Zhu, “Continuous production of
biodiesel fuel from vegetable oil using supercritical methanol
process,” Fuel, vol. 86, no. 3, pp. 442–447, 2007.
[45] B. Jenkins et al., “Combustion properties of biomass,” Fuel
Processing Technology, vol. 54, no. 1–3, pp. 17–46, 1998.
[46] A. Ramadhas, S. Jayaraj, and C. Muraleedharan, “Biodiesel
production from high FFA rubber seed oil,” Fuel, vol. 84,
no. 4, pp. 335–340, 2005.