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Carica papaya stem: A source of versatile heterogeneous catalyst for biodiesel

production and C–C bond formation

Article  in  Renewable Energy · September 2019

DOI: 10.1016/j.renene.2019.09.016

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 Renewable Energy 147 (2020) 541e555

Contents lists available at ScienceDirect

Renewable Energy
journal homepage: www.elsevier.com/locate/renene

Carica papaya stem: A source of versatile heterogeneous catalyst for

biodiesel production and CeC bond formation
Minakshi Gohain a, *, Khairujjaman Laskar b, Atanu Kumar Paul c, Niran Daimary a,
Mrutyunjay Maharana d, Imon Kalyan Goswami a, Anil Hazarika e, Utpal Bora b,
Dhanapati Deka a
a
Department of Energy, Tezpur University, Napaam, 784028, Assam, India
b
Department of Chemical Sciences, Tezpur University, Napaam, 784028, Assam, India
c
Bio-Energy Research Laboratory, Department of Chemical Engineering, Indian Institute of Technology, Guwahati, 781039, Assam, India
d
Centre for Energy, Indian Institute of Technology, Guwahati, 781039, Assam, India
e
Sophisticated Analytical Instrumentation Centre, Tezpur University, Napaam, 784028, Assam, India

a r t i c l e i n f o a b s t r a c t

Article history: Development of solid mixed oxide catalyst from waste biomass is a scarcely studied area. Thus, present
Received 30 January 2019 protocol aims to prepare an environmentally friendly, efficient, renewable and recyclable heterogeneous
Received in revised form base catalyst from Carica papaya stem. The chemical and structural properties of the catalyst were
25 July 2019
examined by Fourier-transform infrared spectroscopy (FTIR), X-ray diffractograms (XRD), Scanning
Accepted 6 September 2019
Available online 9 September 2019
electron microscopy (SEM), Energy Dispersive X-ray spectrometry (EDX), Transmission Electron Micro-
scopy (TEM) and Brunauer-Emmett-Teller (BET) analysis. The CO2-TPD and Hammett indicator test was
conducted to determine the basicity of the prepared catalyst. The study revealed the presence of alkali
Keywords:
Carica papaya stem
and alkaline earth metals that provide the basic sites to facilitate transesterification reaction for biodiesel
Waste production and formation of benzylidenemalononitrile (BMN). The conversion of the waste cooking oil
Heterogeneous catalyst (WO) and Scenedesmus obliquus (SO) lipid to biodiesel was confirmed by the NMR and Gas chroma-
Biodiesel tography Mass Spectroscopy (GC-MS) technique. Biodiesel conversions of 95.23% and 93.33% were
Knoevenagel condensation achieved using 2 wt % catalyst loading under optimized reaction conditions for WO and SO respectively.
Reusing the catalyst showed a slight drop in activity after 6 repeated uses. The reported catalyst has
shown its potential as an alternative and cheaper green solid catalyst for biodiesel production and
Knoevenagel reaction.
© 2019 Published by Elsevier Ltd.

1. Introduction fuel substitute [3]. Biodiesel is produced by transesterification of

The world has witnessed much of the emphasis on energy and
related issues in the last few decades. The issue of continuous
depletion of fossil fuel reserve along with the increase in fuel prices
has drawn global attention towards the development of alterna-
tives that would be renewable, sustainable, efficient and cost-
effective [1,2]. Different countries have set goals to replace a part
of their energy requirement from renewable sources; biodiesel
being considered as a frontrunner to be taken up as an automobile
* Corresponding author. Department of Energy, Tezpur University, Napaam,
784028.
E-mail addresses: minakshiigohain@gmail.com, min_ene@tezu.ernet.in
(M. Gohain).
triglycerides of oils or fats with alcohol (methyl or ethyl) in the
presence of a suitable catalyst [4,5].
Researchers have reported biodiesel as an oxygenated, biode-
gradable and non-toxic fuel [6,7] Although biodiesel has been re-
ported as a potential substitute for petroleum diesel, much of the
works involve homogeneous catalyst for its synthesis which is
chemically synthesized and is toxic as well as corrosive in nature
[8]. Use of homogeneous catalyst leads to additional cost in
wastewater disposal generated during its separation from the re-
action mixture [9]. On the other hand, the heterogeneous solid
catalyst has been reported to be advantageous due to its insolubility
in solvent or esters and hence can easily be recovered and reused
[10].
In recent years, the utilization of eco-friendly and reusable

https://doi.org/10.1016/j.renene.2019.09.016
0960-1481/© 2019 Published by Elsevier Ltd.
542 M. Gohain et al. / Renewable Energy 147 (2020) 541e555
heterogeneous catalyst has emerged as a major constituent of green
chemistry [11]. Solid acids such as sulfated zirconia [12,13], sulfo-
nated carbons [14e16], Amberlyst-15 [17] have attracted a lot of
attention as an effective catalyst for biodiesel production. But, in
the context of sustainability, economy and ecofriendly, the use of
renewable catalysts prepared from biomass have been increasingly
targeted. Waste biomass has been fabricated to prepare acid and
alkali catalysts using activated carbon [18,19] as catalyst support. A
number of works on the preparation of heterogeneous catalyst
from waste biomass viz. coconut shell [20], palm shell [21], wood
ash [22], deoiled cake waste [23] etc., have been reported. Activated
carbon support based catalyst provides more specific surface area
and pores for active species which results in excellent catalytic
ability. But, the cost of production of such catalyst must be factored
in catalyst fabrication such as high carbonization temperature and
wasteful chemical reaction during functionalization of the activated
carbon. However, CaO based heterogeneous catalysts have been
extensively synthesized without any chemical functionalization
from renewable sources like an eggshell [24], waste crab shell [25],
etc. In this context, mixed oxide catalysts from waste biomass have
drawn little attention.
The main problem associated with transesterification reaction
using heterogeneous catalyst is the deactivation of the catalyst with
time generally encountered when used oils are involved which may
be due to poisoning, coking, sintering, and leaching [26,27]. Het-
erogeneous catalyst should possess some hydrophobic character to
support triglycerides adsorption and to avoid deactivation of cat-
alytic sites by strong adsorption of polar byproducts such as glyc-
erol and water [28,29]. Reported literature suggests that the
addition of metals onto the catalyst surface can improve its hy-
drophobicity [30e33]. To enhance the catalytic efficacy biomass
containing metals can be exploited as a forth runner to prepare
such catalyst without any chemical fabrication as a part of sus-
tainable development.
With the advancement in medicinal and pharmaceutical
chemistry, higher attention has also been paid towards the devel-
opment of environment-friendly processes that employ nontoxic
reagents, solvents and catalysts [34]. The Knoevenagel condensa-
tion is one of the most efficient and widely used methods for CeC
bond formation. Over the past years, various heterogeneous cata-
lysts have been developed for Knoevenagel condensation including
ion exchange resins, mesoporous zirconia [35], chitosan bio-
hydrogel [36] etc. Several studies [37] suggest the formation of
BMN and widespread applications of such moiety inspire for the
development of a newer protocol.
Papaya plant has been grown extensively in most of the coun-
tries including tropical and subtropical regions of the world. Papaya
fruit has high energy value as well as it contains a lot of vitamins
and minerals. Papaya plant has been extensively used for the
biochemical synthesis of different pharmaceutical compounds
[38,39]. In 2017, the total world production of papaya was
13,016,281tonnes. India is leading in papaya production with
45.64% of the world total [40]. With such a large amount of papaya
produced, and an estimated 30e50% cull rate, there is a large
amount of agricultural waste produced [41]. The area under papaya
cultivation in India increased from 63% i.e. 45.2 thousand hectares
in 1991e1992 to 73.7 thousand hectares in 2001e2002 [42]. There
are around 1700 papaya plants per acre [42], where stems are
generally 5e10 m long. Cultivators discard the stem of papaya plant
after they find it of no use for productivity and then, the stem be-
comes waste.
Owing to this, present work emphasizes utilization of waste
(discarded papaya stem) as a source for the synthesis of the bio-
catalyst. To the best of our knowledge, it is the first study to explore
Carica papaya stem as a source of heterogeneous biocatalyst which
would be non-toxic, cost effective, renewable, recyclable and
environmentally friendly in nature having widespread application
i.e. for transesterification as well as Knoevenagel condensation
reaction. Thus, a newer approach for the preparation of green
heterogeneous solid base catalyst under the protocol of bio-waste
utilization has effectively been investigated which meets the
widespread scope of chemical transformation.
2. Experimental
2.1. Materials
Carica Papaya stem and WO were collected from the nearby
locality. The SO was obtained from Gauhati University, India.
Chemicals of analytical grades used in the present work were
purchased from Sigma Aldrich and used without further
purification.
2.2. Extraction of lipid
The extraction of lipid from SO dried biomass was carried out
followed by Bligh and Dyer method [43]. Dried biomass sample was
weighed and homogenized in a mortar and pestle using 0.1e0.5 g of
anhydrous Na2SO4 and 1e2 mL of 2% butylated hydroxytoluene
(BHT) (2.04 g of BHT in 100 mL CHCl3). Total lipid was extracted
from the homogenized powder with 5e10 mL mixture of CHCl3:
MeOH (2:1). The residue was extracted with chloroform until it
became colorless. The extracts were mixed together, filtered and
then transferred to a separating funnel. Then 0.9% NaCl solution (1/
3 of the volume) and excess CHCl3 was added to the separating
funnel, mixed thoroughly and kept undisturbed overnight at room
temperature. A clear biphasic layer was observed. The lower layer
(CHCl3) containing the lipid component was collected in a clean
glass vial. The upper layer containing the methanol-water layer was
washed twice with chloroform and collected similarly. All the
collected chloroform layers were mixed together and were evap-
orated in a water bath at 60
C and finally dried in desiccator in
presence of anhydrous Na2SO4.
2.3. Catalyst preparation and its characterization
Carica Papaya stem was cut into small pieces to speed up the
drying process, washed thoroughly using double distilled water
and then dried in an oven at 80
C for 48 h till constant weight. The
dried Carica Papaya stem (CPS) pieces were ground and sieved to a
fine powder. The sieved powdered stem was calcined in a porcelain
crucible placed in a muffle furnace for 4 h at a temperature of
700
C. The calcinated Carica Papaya stem (CCPS) was stored
properly for further use.
The FTIR spectra were measured using Nicolet (Impact 410) on
KBr pellets in 4000-500 cm1 wavenumber range. The XRD of CPS
and CCPS was analyzed by a Rigaku miniflex diffractometer in 2q
range 10e80
(CuKa radiation, l ¼ 1.5406 Å) at 2
scanning rate.
The BET sorption isotherm method (NOVA 1000E, NOVA WIN,
QUANTACHROME) was used to determine the surface area of the
catalyst. The SEM and EDX study was performed using Jeol, JSM-
6290 LV. The TEM study was analyzed using JEOL, JEM-2100 Plus
Electron Microscope, Japan. The Hammett indicator method was
used to determine the basicity. The basicity was also measured by
temperature programmed desorption of CO2 (Autochem 2920,
micrometrics). To remove adsorbed water molecules and other
impurities the sample was pre-treated with Helium gas at 350
C
for 1 h, followed by cooling to room temperature. The CO2
desorption was monitored in the temperature range of
50
Ce670
C. The static contact angle of the catalyst pellet with
 M. Gohain et al. / Renewable Energy 147 (2020) 541e555
Fig. 1. CO2 TPD profile of CCPS.
water was measured using a contact angle meter (Holmarc Opto-
Mechatronics, HO-IAD-CAM-01B). The wettability of CCPS, deno-
ted by contact angle (q) of a water droplet, is given by Young's
equation [Eq. (1)]:
gSV  gSL
cosq ¼
gLV
Where,
gSV ¼ Interfacial surface tension of solid (V)
gSL ¼ Interfacial surface tension of liquid (L)
gLV ¼ Interfacial surface tension of gas vapor (V)
For reusability analysis, the reaction mixture was centrifuged
(3500 rpm) and washed with methanol (MeOH), to recover the
catalyst and to remove impurity. The catalyst was then dried in an
oven at 120
C, for 3 h and experiments were repeated using the
recovered catalysts at required parameters [44].
Fig. 2a. . The N2 adsorption-desorption isotherm of CCPS.
543
2.4. Transesterification procedure
The WO was pre-treated using H2SO4 to reduce the acid value
which was found to be 9.18 mg KOH/g. The acid number of WO after
pre-treatment got reduced to 1.16 mg KOH/g. The acid value of SO
lipid was found to be lower than 2 mg KOH/g i.e. 1.4 mg KOH/g
(1)
which is required for successful transesterification and hence it was
found ideal for effective base-catalyzed transesterification reaction
[45]. In a typical process, 100 mL of WO was poured to a 500 mL
three-necked round bottom flask and heated (100
C) to eliminate
every trace of absorbed moisture. The WO was then cooled down to
60
C. Catalyst, methanol, WO was then mixed to the reactor under
reflux and the reaction continued for desired reaction parameters
[46]. To ensure proper mixing of MeOH and oil the agitation speed
was maintained at 500 rpm. The reaction mixture was allowed to
cool and transferred to a separating funnel where three distinct
layers were clearly visible. The upper layer was mainly composed of
FAME (fatty acid methyl ester), the middle layer of glycerine and
Fig. 2b. . Pore size distribution curve for CCPS.
544 M. Gohain et al. / Renewable Energy 147 (2020) 541e555

catalyst was the bottom layer. The unreacted MeOH from the upper
fraction was evaporated under reduced pressure. The mixture was
then washed with distilled water (40
C) to eliminate impurities
followed by drying over Na2SO4 (anhydrous) to obtain methyl es-
ters of waste cooking oil (WME).
The 1H and 13C NMR spectra of oil and biodiesel were taken in a
500 MHz NMR spectrometer (Oxford, AS400, China). The GC-MS
analysis was carried out in Agilent GC, 240 Ion Trap.
The efficient conversion of oil to FAME was determined in terms
of % FAME using nuclear magnetic resonance (NMR) technique [47]
using deuterated chloroform as solvent [Eq. (2)].
2X
CMEster ð%Þ ¼  100
3Y
X ¼ Integration value of methoxy protons (-OCH3) at 3.6 ppm
Y ¼ Integration value of a-methylene (eCH2e) protons at
2.3 ppm
2.5. Knoevenagel condensation reaction
The progress of the reactions was monitored by TLC (Thin layer
chromatography) which were carried out on Merck silica gel (60F-
254) plates and visualized under UV light (254 nm). To achieve the
desired products, purification of the reaction mixture was done by
column chromatography using silica gel (60e120 mesh). The 1H
NMR spectra were recorded on a JEOL, JNM ECS NMR spectrometer
(2) operating at 400 MHz in CDCl3, using TMS as an internal standard
and 13C NMR spectra were recorded at 100 MHz in CDCl3 (d ¼ 77.00)
as standard. Chemical shifts (d) are quoted in ppm and coupling
constant (J) are expressed in Hz. The structures of the purified
products were confirmed by NMR spectra (See ESI, S1*).

Fig. 3. The SEM image of CPS (a) and CCPS (b).

Fig. 4. The TEM image of CPS (a, b) and CCPS (c, d).
 M. Gohain et al. / Renewable Energy 147 (2020) 541e555 545

Fig. 5. FTIR spectra of CPS (a) and CCPS (b).

Fig. 6. XRD pattern of CPS (a) and CCPS (b).

2.5.1. Synthesis of BMN derivatives

An oven dried 10 mL RB flask was charged with a mixture of aryl
aldehydes (0.30 mmol), malononitrile (0.50 mmol) and catalyst
(8 wt %) in ethanol (2 mL). The reaction mixture was magnetically
stirred and refluxed at 55
C. On completion of the reaction
(monitored by TLC), the reaction mixture allowed to cool, the
catalyst was separated from the reaction mixture by centrifugation

Table 1
Elemental analysis by EDX.

Elements Mass fraction (%) (Fresh)

K 56.71
Ca 21.08
Na 14.78
Mg 4.41
Si 3.02
Fig. 7. EDX analysis of CCPS.
546 M. Gohain et al. / Renewable Energy 147 (2020) 541e555

and the filtrate was extracted with ethyl acetate (3  10 mL). The exhibit a highly porous structure, indicating its high porosity and
catalyst was washed thoroughly and then allowed to dry for further large specific area. The result is in accordance with the BET findings.
use. The resultant organic layer dried over anhydrous Na2SO4, For heterogeneous processes, highly porous catalyst achieves
evaporated under reduced pressure, and purified by column chro- higher conversion efficiency, similarly higher catalytic sites or
matography (2e4% v/v EtOAc: hexane) to afford the desired
product.
To explore the catalytic efficacy of prepared catalyst the recy-
cling potency of CCPS, for the Knoevenagel Condensation of aryl
aldehydes was tested using the model reaction of benzaldehyde
and malononitrile.

3. Results and discussion

3.1. Catalyst characterization

Hammett indicator test was conducted for basicity determina-

tion [48] and obtained according to color variation. After analysis,
the CPS and CCPS showed a basic strength of 9.8 < H  12.2 and of
9.8 < H  18.4 respectively. The increase in the basic strength after
calcination may be due to thermal activation of the metal carbonate
salts to active metal oxide [49]. Group I alkali metal hydroxide and
group II metal oxide infer higher transesterification activity due to
its higher basicity [50]. Strong bases which can remove protons Fig. 9a. Methanol/oil molar ratio effects on FAME conversion.
from MeOH and develop active methoxy species are responsible for
efficient transesterification [44].
Studies report that basicity of a catalyst is the main key in
improving the transesterification activity where the main param-
eter in higher FAME conversion is the number of strong basic sites
[51]. Fig. 1 depicts the TPD profile of CO2 adsorbed on CCPS. At a
higher temperature region i.e. above 400
C, desorption peak was
seen at 653.85
C, while two peaks were observed at 191.8
C and
309.2
C which could be ascribed to weak CO2 adsorption on OH
groups, moderate CO2 adsorption on metal-oxygen pairs and
strong adsorption on O2 anions [52]. These results strongly sug-
gest that both strong and moderately basic sites are present on the
CCPS [53].
As shown in Fig. 2 a, the N2 adsorption-desorption isotherm of
CCPS exhibited typical type IV and hysteresis loops type H3 ac-
cording to the Brunauer-Deming-Deming-Teller (BDDT) classifica-
tion, which indicates that CCPS is typical of a mesoporous in nature
[54]. The surface area of prepared catalyst (CCPS) was found to be
78.681 m2/g; with pore volume and pore radius of 0.349 cc/g and
1.6074 nm respectively. The surface area was found to be higher
Fig. 9b. Catalyst loading effects on FAME conversion.
than other reported works [22,55]. The corresponding pore size
distribution curve (Fig. 2 b) confirmed that the composite is mainly
mesoporous.
The SEM images (Fig. 3) of CPS and CCPS revealed both meso-
porous and microporous structures similar to the previously re-
ported literature [56]. From Fig. 3, it is clear that both CPS and CCPS

Fig. 8. Hydrophobicity test of CCPS. Fig. 9c. Reaction time effects on FAME conversion.
 M. Gohain et al. / Renewable Energy 147 (2020) 541e555 547

higher surface areas are also essential [57]. Sintering of aggregates
was observed after the calcination of CPS which resulted in
agglomeration (Fig. 3 b), and spongy nature was observed [58].
According to previously reported literature, potassium leaching can
be prevented by calcination, and hence may increase the catalyst
reusability [22].
TEM images for CPS and CCPS showed a highly porous structure,
although they are not morphologically homogeneous (Fig. 4). The
more microporous and less mesoporous structure were evident
after calcination (Fig. 4 c and 4 d) which also supports the images
depicts in SEM analysis (Fig. 4). The microporous structure of the
catalyst provides an adequate external surface which acts as active
sites for rapid mass transfer for the transesterification process [55].
Fig. 5 shows the FTIR spectra of CPS and CCPS. Characteristic
bands at 3384 cm1 and 669 cm1 were attributed to the stretching
vibrations of O:H and KeO bonds respectively. The band at
1655 cm1, 1385 cm1, and 1129 cm1 are due to carbonate CO vi-
brations, which indicate the existence of carbonate (CO3). The band
at 2400-2000 cm1 are ascribed to N:O:K bonds (N¼ Mg, Si, etc).
The absorption band at 550 cm1 and 1000 cm1 is due to Ca:O,
K:O stretching and Si:O:Si bonds respectively [58,59] (Fig. 5 a and
5 b). A strong characteristic peak at 1385 cm1 denotes the pres-
ence of K2CO3 which is prominent only in the CBPA due to car-
bonates produced by the adsorption of atmospheric CO2 onto metal
oxides [22] (Fig. 5 b).
The occurrence of crystalline compounds in CPS and CCPS were
identified by XRD analysis (Fig. 6) wherein calcium and potassium
compounds in carbonates, oxides, sulfides, and silicates forms were
observed (Fig. 6 a and 6 b). Increase in potassium compounds can
be seen after calcination (Fig. 6 b) which is depicted by a change in

Fig. 10. Reusability of CCPS in biodiesel production.

Fig. 11. FTIR spectra of reused CCPS catalyst.

548 M. Gohain et al. / Renewable Energy 147 (2020) 541e555

intensity for potassium diffraction lines which had strong basic 3.3. Recycling and reusability of CCPS
sites [60] which is also confirmed by the K2CO3 dominance in FTIR
spectra of CCPS (Fig. 6 b). Strong characteristic diffraction lines Economical application of catalyst for biodiesel production de-
(Fig. 6) of K2O and K2CO3 were observed at 2q ¼ 25, 26, 31, 33, 41, mands recycling and non-leaching capacity of the catalyst [69].
44, 46 and the diffraction lines observed at 2q ¼ 30, 39, 43, 47 are MeOH/oil molar ratio of 9:1, CCPS of 2 wt % for 3 h maintaining the
due to CaO existence.35 Other small diffraction lines were also temperature of 60
C and 600 rpm was taken as the optimized re-
observed corresponding to KCl, K2SO4, K2MgSiO4 (See ESI, S14*). action parameters (Fig. 10). Reduced FAME conversion after the
The EDX analysis (Fig. 7) (Table 1) strongly supported the find- fourth cycle may be due to the leaching of active sites. Change in the
ings of XRD and FTIR which revealed a high distribution of K, Ca, Na, accessible basic sites due to active metal components lost present
Mg and Si oxides. in the catalyst or loss of the surface area of the base catalysts is
It was seen from the results that K is the major ingredient and basically the main reason for solid base catalysts deactivation. Here,
K2O being a strong base is mainly responsible for the basicity of the most important reason for the deactivation of the catalyst is due
CCPS. to the K leaching, as K2O is significantly soluble in glycerol and
The surface hydrophobicity was measured according to the methanol. The K and Ca have a tendency to get leached more
water contact angle (Fig. 8). The surface wettability can be divided readily than other elements [70]. Loss in catalyst quantity during
into four different categories: superhydrophilic (q < 10
), hydro- transfer between each successive cycle might have resulted in
philic (10
< q < 90
), hydrophobic (90
< q < 150
), and super- reduced conversion. Another reason for reduced FAME conversion
hydrophobic (q > 150
) [33]. The CCPS exhibited a hydrophobic may be that the inert species has absorbed the available active sites
nature (q ¼ 106.70
). or has reacted to form other less active species. The trans-
esterification reaction is not only catalyzed by basic sites present on
the catalyst surface but also sometimes by soluble substances [71].
3.2. Optimization of parameters for biodiesel synthesis The recycled catalyst after the fifth cycle was tested to analyze
the leaching of K and Ca from CCPS during successive reaction cy-
One of the essential factors influencing the conversion of oil to cles (Fig. 11).
FAME is alcohol/oil molar ratio [61]. Various operating parameters The peak at 1389 cm1 and 1000 cm1 became very weak in the
such as quality of the oil used in the reaction and the ability of the reused CCPS which signifies the loss of K and Si resulting in the
catalyst to catalyze are also associated along with. Influence of availability of lower basic sites (Fig. 11). The bands at 1050 cm1 and
molar ratio of methanol/oil i.e. 3:1 to 12:1 on FAME conversion was
studied and found that the conversion % was high with higher
MeOH/oil molar ratio (Fig. 9a). Catalyst loading was kept at 2 wt %
and maintaining temperature (60
C, 3 h). A higher amount of
methanol promotes methoxide formation which helps in shifting
the reaction equilibrium to forward direction but, it may also result
in reversible transesterification [62] depending on the parameters
as seen in case of MeOH/oil molar ratio 15:1. The reason might be
that glycerol would have chiefly dissolved in too much methanol
and consequently inhibiting the transesterification reaction. The
optimum MeOH/oil molar ratio was found to be 9:1.
Fig. 9b shows the influence of different loading of catalyst on
biodiesel conversion. Various loading of CCPS was employed for the
conversion of WO to WME. In this study, the transesterification
reaction was performed with MeOH/oil molar ratio of 9:1 for 3 h.
The catalyst amount was varied from 1 to 4 wt % maintaining the
temperature at 60
C (Fig. 9b). At 1 wt % catalyst loading 85% FAME
conversion was achieved which may be due to the availability of a
Fig. 12. XRD spectra of reused catalyst.
less number of basic sites. As the catalyst loading increases the
FAME conversion increased and then remains constant. With
higher catalyst loading the number of active sites increases [45,63],
but beyond a certain optimum catalyst amount the biodiesel con-
version remains constant [64,65]. Higher concentrations of catalyst
might have made the reaction mixture more viscous which has
resisted the mass transfer [66] and since the reaction is base
catalyzed, saponification side reaction might have induced result-
ing in lower FAME conversion [67].
Influence of time on FAME conversion was examined using 9:1
(MeOH to oil molar ratio) and optimum catalyst amount of 2 wt %
(Fig. 9c). Sufficient contact time provides ample contact among the
reactants and catalyst resulting in the successful transesterification
reaction [64]. The reaction was carried out for 5 h and FAME con-
version was observed after every 1 h. The conversion speed is
usually slow at first during transesterification owing to slow
dispersion of triglycerides into the methanol phase. As the reaction
progresses the FAME i.e. generated acts as cosolvent and hence
enhance the miscibility of triglycerides and methanol resulting in
faster conversion until the reaction attains equilibrium [68]. Fig. 13. The N2 adsorption-desorption isotherm of reused CCPS.
M. Gohain et al. / Renewable Energy 147 (2020) 541e555 549

Fig. 14. 1H NMR spectra of WO (a) and WME (b).

550 M. Gohain et al. / Renewable Energy 147 (2020) 541e555

13
Fig. 15. C NMR spectra of WO (a) and WME (b).
 M. Gohain et al. / Renewable Energy 147 (2020) 541e555 551

Fig. 16. GCMS chromatogram of WME.

at 2800 cm1 exhibits eC-O (primary alcohol) and CeH stretching
indicating calcium methoxide was formed onto the surface of CCPS
as CaO reacts with glycerine and methanol to produce calcium
methoxide. The band at 1750 cm1 indicates esters adsorption on
CCPS. The Ca(OCH3)2 and absorbed esters blocked the pores of the
catalyst which lowered the mass transfer during the reaction
resulting in lower FAME conversion [72].
The XRD analysis of the recovered catalyst was investigated after
the sixth run (Fig. 12), and a sharp decrease in the intensity of
potassium oxide was observed. This clearly confirmed that

Table 2 Table 3
Fatty acid methyl esters composition of WME. Fuel properties of the feedstock.

Retention Time Component Property WO SO

21.392 min Propanoic acid, methyl ester Acid value (mg KOH/g) 1.18 1.4
27.517 min 8,11-Octadecadienoic acid, methyl ester Iodine value (g I2/100 g) 127 130
27.759 min Propionic acid, methyl ester Kinematic Viscosity (mm2/s, at 40
C) 31 30
27.901 min 9-Octadecenoic acid, methyl ester, Density (gm/cm3at 15
C) 0.9 0.9
28.239 min 6,9-Octadecadienoic acid, methyl ester Cloud point (
C) 7 5
28.846 min 9, 12, 15-Octadecatrieonic acid, methyl ester Pour point (
C) 2 1

Fig. 17. 1H NMR spectrum of SO biodiesel.

552 M. Gohain et al. / Renewable Energy 147 (2020) 541e555

potassium oxide played a major role in FAME conversion due to its
high basicity.
The spent catalyst was also analyzed for BET (Fig. 13), and a
decrease in the surface area was observed i.e. 61.973 m2/g. The
decrease in the surface area and pore volume is related to the
partial blocking of the pores by Ca(OCH3)2 and absorbed esters as
seen in Fig. 11. The BET surface area data of the used CCPS, support
the hypothesis of pore structure collapse for the used samples [73].
Biodiesel synthesis form SO lipid was studied using the CCPS
catalyst to test its versatile catalytic activity. Successful FAME
conversion of 93.33% was achieved with SO using 9:1 methanol/oil
molar ratio, catalyst loading of 2 wt % within 3 h. The 1H NMR of
Scenedesmus obliquus biodiesel (SOB) is shown in Fig. 17.
The physicochemical properties of the WO, SO and WME, SOB
are shown in Table 3 and Table 4 respectively. The physicochemical
properties of WME meet the FAME standard specifications.

3.4. Biodiesel characterization 3.5. Optimization condition for Knoevenagel reaction

The 1H and 13C NMR spectroscopy confirms the WO and WME.
The presence of glyceridic protons in the range of 4.0e5.2 ppm in
1
H NMR is the characteristics of triglycerides present in WO
(Fig. 14a) which is totally absent in the WME (Fig. 14b). The methyl
ester moiety protons at 3.66 ppm and a-carbonyl methylene groups
at 2.30 ppm are due to methyl ester formation i.e. WME (Fig. 14b). A
chemical shift at 5.3 ppm is due to the alkene proton which signifies
that the main component of WO is unsaturated fatty acid and for
WME is methyl ester respectively.
Fig. 15 (a) and Fig. 15 (b), shows the 13C NMR spectra of WO and
WME respectively. Carboxyl carbons of the ester molecules in tri-
glyceride are depicted at 173.28 ppm, 172.87 ppm and at
68.90 ppm, 62.12 ppm were attributed to carbonyl methylene
groups (Fig. 15 a). The WME showed only the presence of carboxyl
carbon at 174.30 ppm chemical shift (Fig. 15 b). The methoxy carbon
of methyl esters (WME) can be clearly observed at the chemical
shift of 51.42 ppm (Fig. 15 b) which confirms that WO was suc-
cessfully transformed to biodiesel [57].
The WME chromatogram has been presented in Fig. 16. Various
methyl esters peaks were observed at different retention time as
shown in Table 2.
To optimize the reaction condition for the titled compound, an
investigation has been done by changing the solvent system and
results summarized in Table 5. The reaction of benzaldehyde
(0.30 mmol) and malononitrile (0.50 mmol) at 55
C in presence of
CCPS to form compound 3a (Table 6) was selected as a model re-
action. Initially, the reaction was allowed to stir under reflux, the
prolonged reaction time and lesser yield (Table 5, entries 1, and
3e6) were observed. The yield of the product was good in protic
solvents like MeOH and iPrOH (Table 5, entries 2 and 7). However,
maximum yield (93%) of the product with less reaction time was
obtained in EtOH (Table 5, entry 9).
In the present study, a series of benzylidenemalononitrile
(BMN) derivatives (3a-k) (Table 6) have been synthesized using
environmentally benign catalyst (CCPS). Table 6 shows the cat-
alytic merit of formation of BMN derivatives in high yield, with a
short span of time (11e32 min) at 55
C. In view of high catalytic
efficacy of CCPS towards Knoevenagel condensation of aryl al-
dehydes with malononitrile, substituted benzaldehydes were
studied under optimized reaction conditions. As nucleophilic
addition is a rate-determining step in the Knoevenagel
condensation, electron-withdrawing groups are more reactive

Table 4
Fuel properties of FAME.

Fuel Property WME SOB ASTM D 6751 EN 14214

Acid value (mg KOH/g) 0.06 0.2 <0.80 0.5 max

Kinematic Viscosity (mm2/s, at 40
C) 3.10 4.1 1.9e6.0 3.5e5.0
Density (gm/cm3at 15
C) 0.87 0.86 0.86e0.90 0.85
Cloud point (
C) 6 8 e e
Pour point (
C) 10 12 e e
Flash point (
C) 150 115 93 min 120 min
Carbon residue (% wt) 0.016 0.021 0.050 max 0.3
Calorific value (MJ kg1) 40.30 40 e 35 min
Cetane Number 57 58 47 min 51 min

Table 5
Optimization conditions for Knoevenagel condensation of benzaldehyde with malononitrilea.

b
Entry Solvent Catalyst (mg) Time (min) Yield (%)c

1 H2O 2 120 Trace

2 MeOH 2 120 60
3 CH2Cl2 2 120 Trace
4 CH3CN 2 120 Trace
5 MeOH/H2O (2:1) 2 60 45
6 THF 2 60 40
7 i-PrOH 2 60 55
8 EtOH/H2O (1:1) 2 60 50
9 EtOH 2 12 93
10 EtOH e 180 Trace
a
Reaction condition: Benzaldehyde (0.30 mmol), malononitrile (0.50 mmol), catalyst (8 wt% of substrate) and 55
C.
b
Reaction progress monitored by TLC.
c
Isolated yield.
 M. Gohain et al. / Renewable Energy 147 (2020) 541e555 553

Table 6
Knoevenagel condensation reaction of aryl aldehyde derivatives with malononitrile in the presence of CCPSa.

Entry Substrate Product Time (min)b Yield (%)c

1 12 93

2 12 94

3 11 95

4 11 95

5 15 90

6 17 88

7 18 82

8 13 85

9 14 93

10 15 91

11 32 76

a
Reaction condition: Aldehydes (0.30 mmol), malononitrile (0.50 mmol), catalyst (8 wt% of the substrate) at 55
C.
b
Reaction progress monitored by TLC.
c
Isolated yield.

than that of electron-donating groups [74] in BMN derivatives 4. Conclusion

formation. It is evident from Table 6, electron-withdrawing
groups (-Cl, -Br, eNO2) substituted benzaldehyde resulted in
the higher condensed product (entries 2e4, and 8e10) than
those of electron-donating benzaldehyde derivatives (-CH3,
-OMe) (entries 5, 6 and 7). The successful formation of com-
pound 3k also observed with less yield of the product. Hence,
the reaction of aldehydes with malononitrile, substituents on
benzaldehyde derivatives has a significant role towards catalytic
yield.
3.6. Catalyst recycling
The catalyst was used five times for Knoevenagel condensation
and it was found that the catalyst maintained good activity for a
minimum of five consecutive cycles and loss in the yield can be
tolerated as exhibited in (Fig. 18).
In conclusion, a nature benign, renewable, recyclable, hydro-
phobic solid base catalyst was synthesized from waste Carica
Papaya stem to produce biodiesel from waste cooking oil as well as
Scenedesmus obliquus lipid. The catalyst exhibited the highest effi-
ciency with maximum FAME conversion of 95.23% for waste
cooking oil, 93.33% SO within 3 h. Furthermore, Knoevenagel
condensation reaction, the presented procedure with CCPS toler-
ates a wide range of aryl aldehydes giving corresponding BMN
derivatives (3a-k) in appreciable yields. The reusability analysis
showed that the catalyst still exhibited a good catalytic activity
towards biodiesel production (i.e. conversion >85%) and for
Knoevenagel condensation even after five repeated cycles. The use
of reusable green heterogeneous catalyst, substrate tolerance, re-
action time and high yield make this protocol an energy sustainable
choice to that of reported methods.
554 M. Gohain et al. / Renewable Energy 147 (2020) 541e555
Fig. 18. Recycling data of CCPS in Knoevenagel condensation.
Conflicts of interest
There are no conflicts to declare.
Acknowledgements
M. Gohain thanks DBT, New Delhi, India for providing financial
support (Grant No- DBT/IC-2/Indo-Brazil/2016-19/04). K. Laskar is
grateful to the DST-SERB, India for providing National Post-Doctoral
Fellowship (PDF/2017/001364). We acknowledge SAIC Tezpur
University, CSIR-NEIST Jorhat, CSIR-IIP Dehradun, IIT Guwahati and
Gauhati University for assisting in performing analyses. Authors
also thank Dr. Lakshi Saikia (Sr. Scientist, CSIR-NEIST Jorhat) for
providing the facility and necessary help to carry out the CO2-TPD
analysis.
Appendix A. Supplementary data
Supplementary data to this article can be found online at
https://doi.org/10.1016/j.renene.2019.09.016.
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