Industrial Crops & Products xxx (xxxx) xxxx

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Industrial Crops & Products

journal homepage: www.elsevier.com/locate/indcrop

Biodiesel production using a renewable mesoporous solid catalyst

Bishwajit Changmaia, Putla Sudarsanamb, Lalthazuala Rokhuma,*
a
Department of Chemistry, National Institute of Technology Silchar, Silchar, 788010, Assam, India
b
Center for Sustainable Catalysis and Engineering, Faculty of Bioscience Engineering, KU Leuven, Celestijnenlaan 200f, Heverlee, Belgium

A R T I C LE I N FO A B S T R A C T

Keywords: Heterogeneous solid catalysts have been largely developed for biodiesel production, because of their attractive
Fatty acid methyl ester acid-base properties, strong hydrothermal stability, and efficient recovery/reusability. In this framework, de-
Soybean oil veloping bio-waste derived heterogeneous catalysts has attracted immense attention for several catalytic ap-
Orange peel ash plications, owing to their inexpensive, high abundance, non-toxic, and adequate acid-base properties. In the
Reusability
present work, we investigated the catalytic performance of a biomass-derived orange peel ash (OPA), which
Biomass
contains a porous structure, as a raw heterogeneous catalyst for the transesterification of soybean oil to bio-
diesel. About 98 % conversion of soybean oil to biodiesel was obtained under the optimized reaction conditions
i.e., 6:1 methanol:oil ratio, 7 wt. % catalyst loading, 7 h reaction time at ambient reaction temperature, which
ascribed to the presence of abundant basic sites in the developed OPA catalyst. The catalyst can be reused for five
successive cycles and shows good stability towards the biodiesel production.

1. Introduction of triglycerides, and is mainly produced from vegetable oils, waste

Increasing rate of energy consumption and abnormal climate
change, due to the rapid population growth and the emission of en-
vironmental pollutants (e.g., CO2), respectively, have led to the search
for new, sustainable, and renewable energy sources. Presently, non-
renewable fossil fuels are the major source for the production of energy,
fuels, and chemicals (Sahaym and Norton, 2008; Putla et al., 2019).
Concurrently, the resources of fossil fuels are declining gradually as the
consumption rate is increasing drastically to meet our energy needs. In
addition, fossil fuels emit various greenhouse gases like CO2, S, NOx,
etc., which are the key factors for global warming, a major threat facing
humankind in the 21st century (Agarwal, 2007; Ambursa et al., 2016;
Caliskan, 2017). To minimize the emission of greenhouse gas and to
meet increasing energy demand, the use of an alternative renewable,
sustainable, and safer energy source is essential (Panwar et al., 2011).
Biofuels, like biodiesel and biogas are the excellent sources to meet
the future energy demand (Kumar et al., 2018; Gilbert and Perl, 2008).
Currently, biodiesel, also known as fatty acid alkyl esters (FAMEs), has
attracted much attention due to its biodegradability, low emission of
CO2 and CO, low sulphur content, renewable, and environmental
friendly nature. Moreover, biodiesel is compatible to normal diesel
engine without any modification (Kulkarni et al., 2006; Kralova and
Sjöblom, 2010; Maeda et al., 2011; Ong et al., 2011). It is an ester-
ification product of long chain fatty acids or transesterification product
cooking oils, non-edible oils, etc. (Agarwal and Das, 2001; Ma et al.,
2018).
In particular, biodiesel is largely produced by transesterification of
long chain fatty acids using homogeneous catalysts, like KOH, NaOH,
etc. (Likozar et al., 2016) Although homogeneous catalysts showed
good activity in terms of conversions and yields, their toxic and cor-
rosive nature, problems associated with product purification and as
well as with catalyst recovery and its reusability limit their applications
in chemical industry. Thus, the overall cost of biodiesel production
increases hugely (Likozar and Levec, 2014; Mardhiah et al., 2017). In
recent years, heterogeneous catalysts have attracted much interest as a
potential substitute to homogenous catalysts because of their inter-
esting properties, such as non-toxic, easy separation and recyclable, and
non-corrosive nature (Sharma et al., 2011). Several heterogeneous
catalysts, such as Zn@CaO (Kumar and Ali, 2013), CaO@SnO2 (Xie and
Zhao, 2013), biguanide-functionalized hydroxyapatite encapsulated-γ-
Fe2O3 nanoparticles (Lee et al., 2015), CaO@La2O3 (Xie et al., 2017)
etc. were reported for the production of biodiesel. However, the che-
mical synthesis of such catalysts is quite complicated and often involves
drastic reaction conditions and multi steps, resulting in increased cat-
alyst synthesis costs (Correia et al., 2014). In this context, the use of
waste biomass-derived material as a heterogeneous solid catalyst is an
excellent choice for a more sustainable biodiesel production
(Sudarsanam et al., 2018; Shan et al., 2018).

⁎
Corresponding author.
E-mail address: rokhum@che.nits.ac.in (L. Rokhum).

https://doi.org/10.1016/j.indcrop.2019.111911
Received 8 July 2019; Received in revised form 22 October 2019; Accepted 26 October 2019
0926-6690/ © 2019 Elsevier B.V. All rights reserved.

Please cite this article as: Bishwajit Changmai, Putla Sudarsanam and Lalthazuala Rokhum, Industrial Crops & Products,
https://doi.org/10.1016/j.indcrop.2019.111911
B. Changmai, et al.
In spite of its wide availability and renewable nature, little attention
has been directed towards modification of the waste biomass for im-
proving its catalytic performance. A few studies have reported on the
modification of waste biomass via surface functionalization using con-
ventional bases and acids. In this regard, functionalized coconut husk
(Vadery et al., 2014), palm trunk (Ezebor et al., 2014), wood ash
(Sharma et al., 2012) and rice husk (Zhao et al., 2018) were reported as
heterogeneous catalysts for the production of biodiesel.
Although functionalized bio-waste derived carbon-based solid cat-
alyst has its own merits, functionalization of waste biomass involves
some drawbacks, such as high cost, high temperature for carbonization
and tedious preparation steps, which limits its applications. Hence,
using a raw biomass waste as an effective and recyclable heterogeneous
catalyst is essential for sustainable biodiesel production in industrial
scale. In this line, limited literature reported the application of raw
biowaste (without functionalization) as a heterogeneous catalyst in the
production of FAME (Betiku et al., 2016; Betiku and Ajala, 2014;
Gohain et al., 2017). Recently, our research group has successfully
utilized biowaste, banana (Musa acuminata species (available in
Southeast Asia) peel ash as a heterogeneous catalyst for the production
of biodiesel (Pathak et al., 2018). The catalyst shows excellent activity
with a very high oil conversion of 98.95 %. Despite the high activity of
the catalyst, the reusability of the catalyst limits its application in in-
dustrial scale.
Among all the citrus fruit produced annually, about 75 % is con-
tributed by orange (Citrus sinensis) (Li et al., 2008). The global orange
production is about 49.3 million metric tons in the year 2017-2018.
Therefore, the disposal of waste orange peel is a major concern.
Nonetheless, orange peel is considered as a valuable agricultural bio-
mass waste, composed of cellulose, carbohydrates, fats, etc. (Chutia
et al., 2009). Several reports had been already published regarding the
applications of orange peel in the field of pollution abatement, like
removal of heavy metals from wastewater and production of solid
biofuels (Biswas et al., 2008; Santos et al., 2015). Until now, there are
no literature reports on the production of FAME by using orange peel
ash.
In this present work, in continuation of our interest in the devel-
opment of economic heterogeneous catalysts, green synthetic meth-
odologies (Rajkumari et al., 2017; Das et al., 2016) and renewable
energy (Pathak et al., 2018; Laskar et al., 2018a; Chatterjee et al., 2017;
Laskar et al., 2018b), we used waste biomass (orange peel ash) as a
heterogeneous catalyst for the conversion of soybean oil to biodiesel at
room temperature (RT). The investigated orange peel ash catalyst is
highly abundant, renewable, and cost-effective. In addition, it is easily
prepared by burning the dried orange peel and can be used for biodiesel
production without further modification.
2. Materials and methods
2.1. Chemicals used
Soybean oil was purchased from the local market in Silchar, Assam,
India. Methanol (analytical grade) was purchased from Merck, India.
The chemicals were used without further purification.
2.2. Preparation and characterization of the catalysts
The fresh orange were collected from Silchar, Assam, India. The
peels were separated, washed properly with distilled water, cut into
small pieces and then dried under sun for 3 days. Afterwards, about
50 g of dried orange peels were burnt in open air for 30 min and ground
to produce orange peel ash (OPA) weighing 4.94 g. The structure,
morphology, crystallinity and composition of the resultant catalyst
were characterized by FTIR (Fourier transform infrared spectroscopy),
XRF (X-ray fluorescence), XRD (powder X-ray diffraction), SEM (scan-
ning electron microscope), HRTEM (high resolution transmission
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electron microscope), XPS (X-ray photoelectron spectroscopy), EDX
(energy dispersive X-ray spectroscopy), BET (Brunauer-Emmett-Teller)
and TGA (thermogravimetric analysis) techniques. The FTIR spectra
was taken in a Spectrum 100 spectrophotometer. HRTEM was taken in
an electron microscope JEM-2100 instrument. SEM and element dis-
tribution of the catalyst i.e., EDX were taken in JSM-6360 (JEOL) in-
strument. XRF analysis was performed on Bruker S4 Poinner instru-
ment. XPS analysis was performed using a ESCALAB Xi + instrument.
XRD analysis was performed on an ULTIMA IV. The N2 ad-
sorption–desorption analysis was carried out using a Micromeritics
ASAP 2010. The TGA analysis was performed using SII 6300 EXSTAR
instrument under N2 atmosphere.
2.3. Transesterification of soybean oil
14 g of soybean oil was taken in a round bottom flask, followed by
the addition of 4 mL methanol and 1 g catalyst (7 wt. % w.r.t soybean
oil) and then, stirred at ambient temperature. The progress of the
transesterification reaction was observed by taking thin layer chroma-
tography (TLC). The reaction was completed after 7 h, as confirmed by
TLC. The catalyst was recovered by centrifugation at 3500 rpm for
25 min. Biodiesel and glycerol were separated via separating funnel
followed by evaporation of excess methanol via rotary evaporator.
2.4. Characterization of FAME
The synthesized FAME was characterized by 1H NMR, 13C NMR and
GC–MS (gas chromatography-mass spectrometry) analytic techniques.
1
H NMR and 13C NMR was carried out in Mercury Plus 300 MHz NMR
spectrometer. GC–MS analysis was carried out in JEOL AccuTOF GCV
instrument.
2.5. Reusability of the catalyst
Prior to catalyst reusability test, the catalyst was recovered using
centrifugation, washed with methanol and kept in an oven at 100 °C for
5 h to dry out the catalyst. Reusability test was investigated under the
optimized reaction conditions i.e., 6:1 methanol:oil ratio, 7 wt.% cata-
lyst, 7 h and room temperature.
3. Results and discussion
3.1. Characterization of orange peel (OP) and orange peel ash (OPA)
catalyst
EDX was performed to investigate the elemental composition of the
orange peel (SI, Fig. S1) and the OPA catalyst (Fig. 1A). EDX data shows
the presence of K, Ca, O, C, P, Mg, and Cl in both samples. The ele-
mental distribution along with their atomic wt.% are shown in Table 1.
The wt.% of K and Ca increased from 0.18 % and 0.03 % (in the dried
orange peel) to 14.67 % and 7.34 % (in the OPA), respectively, due to
the burning of organic matters present in the dried orange peel to
produce OPA. Due to the presence of basic sites (e.g., K and Ca) OPA
could show good catalytic activity in the base-catalyzed reactions like
transesterification reaction of soybean oil to biodiesel.
TGA analysis was performed under N2 atmosphere to verify the
stability of the OPA catalyst with temperature. TGA thermogram dis-
plays an initial weight loss of 6 % up to 181 °C, due to the removal of
adsorbed moisture from the catalyst. The further weight loss of the
catalyst under high temperature might be due to the oxidation of the
carboneous materials in the form of CO and CO2 (Chouhan and Sarma,
2013) (Fig. 1B).
To investigate the pore volume, pore diameter and BET surface area
of the prepared catalyst, N2 adsorption-desorption analysis was carried
out. Fig. 1C shows N2 adsorption–desorption isotherm of type IV, which
indicates that the catalyst is mesoporous in nature. BJH model (Fig. 1D)
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Fig. 1. EDX spectrum of OPA catalyst (A), TGA thermogram (B), N2 adsorption-desorption isotherm (C), and BJH pore size distribution (D).

Table 1 Table 2
EDX data for elemental composition of OP and OPA catalyst. Composition of OP and OPA as determined by XRF analysis.
Sl. No Element OP (Atomic %) OPA (Atomic %) Sl. No Compound formula OPA (wt. %)

1 O 42.00 40.86 K2 O 51.64

2 C 57.73 32.50 2 CaO 25.67
3 K 0.18 14.67 3 SiO2 13.24
4 Ca 0.03 7.34 4 MgO 4.76
5 Mg 0.04 2.02 5 P2O5 2.95
6 P 0.01 1.57 6 Na2O 1.81
7 Fe2O3 0.070
8 MnO 0.033
9 TiO2 0.114
depicted high pore density in the mesoporous region centered at
2.85 nm. The pore volume and BET surface area of the catalyst were
found to be 0.428 cc/g and 605.60 m2/g, respectively. Due to the high
FTIR analysis was performed to detect the functional groups present
BET surface area and mesoporous nature of the catalyst, it may show
in the OPA (Fig. 2). The band at 3251 cm-1 represents the stretching
good catalytic activity towards the production of FAME from soybean
frequency of OeH bond, due to the absorption of water molecules from
oil.
the atmosphere. The characteristic peaks at 1447 cm-1, 1064 cm-1 and
To investigate the composition of OPA catalyst, XRF analysis was
876 cm-1 were attributed to carbonate stretching and bending vibration.
performed. The composition of the catalyst listed in Table 2, shows that
The absorption peaks at 708 cm-1 and 608 cm-1 were attributed to KeO
alkaline K2O and CaO are the major components present in the catalyst
and CaOe stretching frequency, respectively.
(OPA). Thus, K2O and CaO could play a major catalytic role in the
XRD analysis was performed to investigate the crystalline compo-
production of biodiesel from soybean oil.
nents present in the catalyst. XRD data (Fig. 3) show the presence of
To investigate the basicity of the catalyst, Hammett indicator
K2O, CaO, K2CO3, CaCO3, MgO, SiO2 etc. The peaks for K2O and K2CO3
method was performed and it was found to be 9.8 < H_ < 12.2 for OPA
were observed at 2θ = 30.106, 41.11, 33.72, and 42.160° (JCPDS file
catalyst. The high basicity of catalyst can be ascribed to the presence of
no. 77-2178 and JCPDS file no. 71-1466). The peaks for CaO and CaCO3
K2O, CaO, MgO, etc., as observed from XRF data (Table 2). Hence, the
were observed at 2θ = 26.007, 39.83, 28.41, and 48.75° (JCPDS file no.
presence of high basic sites can lead to improved catalytic activity of
28-0775 and JCPDS file no. 72-1214). The existence of SiO2 and MgO in
OPA catalyst towards biodiesel synthesis via transesterification reac-
the catalyst was confirmed by the peaks at 2θ = 33.72, 54.37, 43.60,
tion.
and 57.83° (JCPDS file no. 89-3609 and JCPDS file no. 57.83). Thus,

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B. Changmai, et al.
Fig. 2. FTIR spectrum of fresh OPA.
Fig. 3. XRD spectrum of OPA catalyst.
oxides and carbonates of K and Ca are the dominating components in
the catalyst, which supports the XRF data (Table 2).
TEM and SEM were performed to investigate the external surface
morphology and structure of OPA (Fig. 4). The TEM and SEM images
showed well-arranged microporous and mesoporous structure with
some spongy nature of the OPA catalyst.
`To further investigate the elemental composition of the catalyst,
XPS analysis was performed. Fig. 5 shows the wide range XPS spectrum
along with deconvoluted spectra for C 1s, O 1s, K 2p, Ca 2p and Mg 1s.
The catalyst comprises of C, O, K, Ca, Mg, Na, P, etc., as shown in
Fig. 5A. The deconvoluted spectrum for C 1s (Fig. 5B) shows two peaks
at 283.92 eV and 288.53 eV, which can be ascribed to CeC and CO]
bonds, respectively. Fig. 5C shows two peaks for K 2p with binding
energies of 291.73 eV and 294.45 eV, which are ascribed to K in the
form of metal oxides and metal carbonates. Fig. 5D shows two peaks for
Ca 2p with binding energies of 345.94 eV and 349.48 eV, which con-
firms the presence of CaO and CaCO3. Mg 1 s spectrum contains one
peak with binding energy of 1303.72 eV, confirming the presence of
MgO (Fig. 5E). The O 1s spectrum shows two peaks at 530.12 eV and
532.07 eV, which can be ascribed to the presence of oxides and car-
bonates of metals (Fig. 5F). The atomic wt. % of the major elements,
obtained from XPS analysis, present in the OPA catalyst are listed in
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Table 3, which supports the results obtained from both XRF (Table 2)
and EDX data (Table 1).
3.2. Characterization of synthesized biodiesel
Once the transesterification reaction to produce FAME was com-
pleted, the resultant product was confirmed by performing 1H NMR and
13
C NMR analysis. Fig. 6 shows the 1H NMR spectrum of soybean oil
(Fig. 6A) and FAME (Fig. 6B). The appearance of peaks at 4.31 ppm and
5.36 ppm confirms the presence of glyceridic protons and olefinic
protons (Fig. 6A) in soybean oil. While the appearance of a peak at
3.68 ppm and disappearance of peak at 4.31 ppm confirms the forma-
tion of FAME (Fig. 6B). The singlet peak at 3.68 ppm represents the
methoxy protons of FAME and the triplet peak at 2.32 ppm can be at-
tributed for α−CH2 protons. From 13C NMR, the appearance of peak at
51.41 ppm for −OCH3 carbon (SI, Fig. S2B) and disappearance of
glyceridic carbon peaks at 68.89 ppm and 62.08 ppm (SI, Fig. S2A)
confirms the formation of FAME. The percentage yield of soybean oil to
FAME can be determined by using the integration value for methoxy
protons and integration value for α−CH2 protons in the equation de-
rived by Knothe and Kenar (Eq. 1). The percentage yield of FAME was
calculated and it is found to be 98 % at optimized reaction conditions as
discussed in the following sections.
2AMe
C = 100 ×
3ACH2 (1)
Here, C is the percent conversion of soybean oil, AMe is the integration
area of the methoxy protons and ACH2 is the integration area of the
α−CH2 protons.
The chemical composition of the synthesized FAME was obtained by
GC–MS analysis (Fig. 7). Furthermore, the quantitative measurement of
FAME components was calculated by using the peak areas of FAME and
internal standard peak area (methyl heptadecanoate, C17:0). The ob-
tained data was presented in Table 4.
The properties of soybean oil and synthesized FAME were measured
by using standard methods depicted in the Table 5. The properties of
the synthesized biodiesel meets the standard of ASTM D 6751.
3.3. Influence of reaction parameters on soybean oil to FAME conversion
3.3.1. Influence of catalyst loading
The effect of catalyst loading in the conversion of soybean oil to
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Fig. 4. TEM images (A, B) and SEM images (C and D) of OPA catalyst.

Fig. 5. (A) Wide range XPS spectrum and (B), (C), (D), (E), (F) are the deconvoluted peaks of C1s, K 2p, Ca 2p and Mg 1s and O 1s of OPA catalyst, respectively.

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Table 3
XPS data for elemental composition and their corresponding amount (%) of the
catalyst.
Sl. No Elements Atomic wt%
1 O1 s 39.45
2 C1 s 33.07
3 K2p 13.53
4 Ca2p 7.56
5 Mg1 s 2.11
6 P2p 1.23
FAME (Fig. 8) was performed by varying the catalyst amount from 2 wt.
% to 13 wt. % with 1:6 oil:methanol ratio at RT. When catalyst loading
was 2 wt. % the conversion was 76.5 %. Increasing the catalyst loading
to 7 wt. %, about 98 % conversion of oil to FAME was found. Further
increase in catalyst loading, a decrease in the conversion of oil was
observed. This might be due to the initiation of saponification reaction
at higher catalyst loadings, which also makes the reaction mixture more
viscous, resulting in severe mass transfer limitations (Pathak et al.,
2018; Hsiao et al., 2011). Thus, the conversion of oil decreases at higher
catalyst loadings and therefore, 7 wt. % is the optimal catalyst loading
for achieving high conversion of soybean oil to FAME.
3.3.2. Influence of methanol:oil ratio
The significant effect of oil:methanol ranging from 1:3 to 1:12 on
the production of FAME (Fig. 9) was investigated with catalyst loading
of 7 wt.%, 7 h reaction time and at ambient temperature. 1:3 of oil:-
methanol ratio gives only 74 % conversion of FAME. While, 1:6 of
oil:methanol ratio drastically increases the conversion of FAME to 98
%. Further increase in the oil:methanol ratio upto 1:12; it is expected to
exponentially increase the conversion of FAME. However, the conver-
sion decreased to 96 % for 1:12 oil:methanol molar ratio since increase
in the amount of methanol will drive the reaction to backward direction
to form monoglyceride and diglyceride as the transesterification is a
reversible reaction (Laskar et al., 2018a). Thus, 1:6 oil:methanol molar
ratio is the optimized condition for the maximum conversion of soy-
bean oil to FAME.
3.3.3. Influence of reaction time on conversion of soybean oil to FAME
The influence of reaction time on biodiesel production was also
investigated by performing the reaction for different time-period at
optimized conditions (Fig. 10). It was observed that after 7 h it gives 98
% conversion of biodiesel.
3.4. Comparison of other reported heterogeneous catalysts with the present
catalyst
Several literatures were reported on the production of FAME from
soybean oil using heterogeneous catalysts. Comparison of reported
heterogeneous catalysts with the present catalyst is shown in Table 6.
CaO–MoO3–SBA-15 (Xie and Zhao, 2014), CaO/Al2O3 (Pasupulety
et al., 2013), WO3/SnO2 (Xie and Wang, 2013) etc., showed very good
stability and high conversion of soybean oil to FAME, but they have
some drawbacks such as preparation of these catalyst require toxic
chemicals, complex chemical process and high cost. However, several
heterogeneous catalysts, such as chicken manure (Maneerung et al.,
2016), egg shell (Wei et al., 2009), waste carbide slag (Li et al., 2015),
snail shell (Laskar et al., 2018a) etc., can be prepared from natural
waste which can reduce the total cost of the FAME production. Un-
fortunately, preparation of these catalyst requires high calcination
temperature and longer time, which limits their wide applications in
industrial scale. Recently, (Pathak et al. (2018) reported the use of a
banana species Musa acuminata peel ash catalyst for the preparation of
FAME from soybean oil at room temperature. Despite the high activity
of the catalyst, the catalyst shows only 52 % conversion after the 4th
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Industrial Crops & Products xxx (xxxx) xxxx
run. In contrast, orange peel ash catalyst shows very high activity and
stability towards the FAME production at room temperature and can be
reused for 5 catalytic cycles with high percentage conversion.
3.5. Reusability test of OPA catalyst
Catalyst reusability is a very important factor to use the catalyst in
commercial scale and industrial processes. Reusability test was per-
formed for 5 successive cycles under the optimized reaction conditions
i.e., 6:1 methanol:oil ratio with 7 wt.% at RT for 7 h (Fig. 11). The
conversion of FAME after each cycle was recorded and it was observed
that conversion decreases in each cycle and after the 5th cycle the
conversion of FAME was only 85 %. This might be due to the slight
leaching of active sites of the catalyst during the reaction and/or weight
loss of the catalyst during recovery/purification steps.
The XPS analysis of the recovered catalyst after 5th cycle was per-
formed. The wide range XPS spectrum and deconvoluted spectra of K
2p, O 1s and Ca 2p (SI, Fig. S3), show a significant drop of K, O and Ca
atomic wt. % from 13.53 %, 39.45 % and 7.56 % to 11.32 %, 34 % and
5.95 %, respectively. The slight loss of K and Ca leads to the slight
decrease of catalytic activity towards the transesterification reaction
and hence, the yield of FAME was considerably decreased to 85 % after
the 5th catalytic cycle. Thus, we can conclude that K and Ca play a
major catalytic role in the production of FAME.
To investigate the morphology and structure of the recovered cat-
alyst after the 5th cycle, SEM and TEM analyses were performed (SI,
Fig. S4), which show an irregular surface, morphology and structure of
the catalyst after the 5th cycle.
To investigate the functional groups present in the recovered cata-
lyst after the 5th cycle, FTIR analysis was performed (SI, Fig. S5 A). An
absorption peak was observed at 3328.31 cm-1, which is due to the
presence of moisture absorbed by the catalyst. The peak at 2924.92 cm-
1
could be attributed for C–H stretching of Ca(OCH3)2, which is formed
in little amount on the catalyst surface, due to the reaction of CaO with
methanol and glycerin (Gohain et al., 2017). The peaks at 1430.78 cm-1,
1069.53 cm-1 and 874.86 cm-1 could be attributed for carbonate
stretching and bending vibration. The spectra also show the peaks at
718 cm-1 and 576.84 cm-1, which are characteristics of KeO and CaOe
stretching vibrations.
The chemical composition of the recovered OPA catalyst after 5th
cycle, investigated via EDX analysis (SI, Fig. S5B), shows a significant
loss of K, Ca and O wt. %, from 14.67 %, 40.86 % and 7.34 % to 11.95
%, 34.64 % and 6.10 %, respectively. Due to the slight loss of major
catalytic components, such as K, Ca and O, the conversion of soybean
oil decreased to 85 % after 5th cycle.
4. Conclusions
In conclusion, we for the first time reported the application of or-
ange peel ash (OPA) as a raw heterogeneous catalyst for sustainable
production of biodiesel via transesterification of soybean oil at room
temperature. The mesoporous structure and the high BET surface area
of the OPA (605.60 m2/g) enhanced its catalytic activity towards
transesterification reaction. Potassium and calcium in the form of their
oxides are the major components present in the catalyst, which makes
the catalyst highly basic. Owing to heterogeneity and basic nature, OPA
catalyst can potentially replace conventionally used homogeneous basic
catalysts for biodiesel production. Moreover, the catalyst was used for
biodiesel production without any functionalization or post-modifica-
tion. Our catalyst has the advantages of being renewable, non-toxic,
biodegradable, safe to handle and carbon neutral. Although the burning
of orange peel produces carbon dioxide, it is considered ‘carbon neutral’
as orange trees absorb carbon dioxide during its whole life cycle.
Hence, our catalyst has a huge impact on conserving the environment
as compared to chemically synthesized catalysts which are often highly
toxic, polluting, unstable and largely non-biodegradable. In addition,
B. Changmai, et al. Industrial Crops & Products xxx (xxxx) xxxx

Fig. 6. 1H NMR of soybean oil (A) and FAME (B).

owing to its wide availability at low cost, the application of bio-waste scale.
materials as a catalyst source not only complements the potential re- The authors declare the following financial interests/personal re-
cycling the natural waste resources but also reduce the total cost and lationships which may be considered as potential competing interests:
negative environmental impact of biodiesel production for industrial

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Fig. 7. GC–MS spectrum of FAME.

Table 4
Components present in the resultant FAME along with their percentage weight
and retention time (R.T.).
Entry R.T. Name of components Corresponding acids Amount (%)

1 18.05 Methyl palmitate C16:0 11.63

2 20.13 Methyl oleate C18:1 25.32
3 21.44 Methyl linoleate C18:2 54.34
4 24 Methyl cis-11-eicosenoate C20:1 1.27
5 24.36 Methyl eicosenoate C20:0 2.56
6 27.05 Methyl docosanoate C22:0 4.88

Table 5
Physico-chemical properties of soybean oil and soybean oil biodiesel.
Properties ASTM test ASTM limits Soybean oil Soybean oil
method for biodiesel biodiesel

Kinematic viscosity D 445 1.90-6 32.6 5.88

(cst at 40 °C) Fig. 9. Influence of oil:methanol molar ratio for the transesterification of soy-
Flash point (°C) D 93 < 93 317 146 bean oil to biodiesel. Reaction conditions: catalyst loading of 7 wt. %, reaction
Cetane number D 6890 ≥47 37.9 51 time of 7 h and room temperature.
Cloud point (°C) D 2500 −3 to 12 −9 2
Pour point(°C) D 97 −15 to 6 12 −0.2
Density (g cm−3) D 1448–1972 0.86-0.900 0.93 0.86
Calorific Value D240 37.27 39.6 38.2
(MJ/kg)

Fig. 8. Influence of catalyst loading for the transesterification of soybean oil to
biodiesel. Reaction conditions: 6:1 of methanol:oil ratio, Catalyst loading of
7 wt. % and RT.
Fig. 10. Influence of reaction time for the transesterification of soybean oil to
biodiesel. Reaction conditions: 6:1 of methanol:oil ratio, catalyst loading of
7 wt. % and RT.
Declaration of Competing Interest
The authors declare that they have no known competing financial
interests or personal relationships that could have appeared to influ-
ence the work reported in this paper.

8
B. Changmai, et al. Industrial Crops & Products xxx (xxxx) xxxx

Table 6
Comparison of other reported heterogeneous catalysts with the present catalyst.
Entry Catalyst Methanol/oil molar ratio Catalyst amount (wt. %) Temperature (°C) Time (h) Conversion (%) Reference

1 CaO–MoO3–SBA-15 50:1 6 63 50 83.2 (Xie and Zhao, 2014)

2 CaO/Al2O3 9:1 3 150 3 90 (Pasupulety et al., 2013)
3 WO3/SnO2 30:1 5 110 5 79.2 (Xie and Wang, 2013)
4 Chicken manure 15:1 7.5 65 3 90 (Maneerung et al., 2016)
5 Egg shell 9:1 3 65 3 95 (Wei et al., 2009)
6 Waste carbide slag 9:1 1 65 0.5 91.3 (Li et al., 2015)
7 Duck egg shell 10:1 10 60 1.2 94.6 (Yin et al., 2016)
8 Snail shells 6:1 3 RT 7 100 (Laskar et al., 2018a)
9 Banana peel ash 6:1 7 RT 4 98.95 (Pathak et al., 2018)
10 Orange peel ash 6:1 7 RT 7 98 Present work

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