Waste Management 102 (2020) 212–221

Contents lists available at ScienceDirect

Waste Management
journal homepage: www.elsevier.com/locate/wasman

Towards sustainable biodiesel and chemical production: Multifunctional

use of heterogeneous catalyst from littered Tectona grandis leaves
Minakshi Gohain a,⇑, Khairujjaman Laskar b, Hridoyjit Phukon c,d, Utpal Bora b, Dipul Kalita c,d,
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
Cellulose Pulp and Paper Group (Material Sciences and Technology Division), North East Institute of Science and Technology, Jorhat 785006, Assam, India
d
Academy of Scientific and Innovative Research, Council of Scientific and Industrial Research - North East Institute of Science and Technology, Jorhat 785006, Assam, India

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

Article history: Waste biomass derived heterogeneous catalyst is an excellent alternative to chemically synthesized cat-
Received 9 September 2019 alysts. In this work, calcined Tectona grandis leaves were proposed as an eco-friendly, renewable and low
Revised 24 October 2019 cost heterogeneous base catalyst. The prepared catalyst was examined by FTIR, XRD, XPS, SEM, EDX, TEM,
Accepted 27 October 2019
TGA, BET and Hammett indicator test. The catalyst has an appealing nature towards various chemical
transformations due to its basic surface sites provided by alkali and alkaline earth metals. The efficiency
of the catalyst was successfully investigated by its application in biodiesel production. The products were
Keywords:
confirmed by 1H and 13C NMR. 100% FAME conversion was attained using a catalyst loading of 2.5 wt%
Waste biomass
Tectona grandis leaves
under optimized reaction parameters. The catalyst was further explored for Knoevenagel condensation
Renewable reaction, in which it showed its effectiveness and recyclability towards the formation of benzylidene-
Biodiesel malononitrile derivatives of aryl aldehydes. Thus, it is a potential ‘green catalyst’ derived from waste bio-
Knoevenagel condensation mass without any addition of chemicals that can replace the industrial base catalysts used for biodiesel
production and Knoevenagel reaction and makes the protocol environmentally benign.
Ó 2019 Elsevier Ltd. All rights reserved.

1. Introduction esterification reaction using homogeneous catalyst (NaOH, KOH,

Depletion of fossil fuels, increasing concerns about environmen-
tal pollution and greenhouse gases emission has led to the explo-
ration of sustainable sources of energy (Li and Guo, 2017;
Sharma et al., 2009; Lardon et al., 2009). Among the alternatives,
renewable and sustainable biodiesel has the key advantage of
using the existing current technology for diesel fuels (Teo et al.,
2018). Biodiesel derived from edible or non-edible oils are a poten-
tial alternative for diesel fuels which is biodegradable, non-toxic
and renewable (Lardon et al., 2009; Agarwal et al., 2018; Rafiei
et al., 2018). But the current conventional method used for biodie-
sel synthesis is not sustainable due to use of edible vegetable oils
as feedstocks which accounts for more than 70% of the total pro-
duction cost (Piker et al., 2016). Low cost and available feedstocks
like waste cooking oil (Gohain et al., 2019; Tan et al., 2019; Xiong
et al., 2019), jatropha and palm oil should be used to replace the
food grade vegetable oils for commercial biodiesel synthesis
(Janaun and Ellis, 2010). It is generally synthesized through trans-
⇑ Corresponding author.
E-mail address: minakshiigohain@gmail.com (M. Gohain).
CH3CH2ONa, H2SO4 etc), which are corrosive for the reactors
(Sano et al., 2017), separation of the catalyst from the reaction mix-
tures is costly and chemically wasteful (Ma and Hanna, 1999;
Noureddini and Zhu, 1997) as well. Solid catalysts based on ZrO2
(Ajala et al., 2015), SrO (Liu et al., 2007), ZnO (Xie and Li, 2006,
Fe3O4 (Tang et al., 2012) etc., have been used in biodiesel synthesis
however the use of biomass derived catalyst is highly desirable
from the perspective of sustainability and economy (Steen et al.,
2010).
Activated carbon prepared from waste biomass has been exten-
sively fabricated by functionalization with acids or bases to pre-
pare various solid catalysts such as deoiled cake (Konwar et al.,
2014; Toda et al., 2005), modified rice (Roschat et al., 2016) and
peat as support (Wang et al., 2017). Carbon based catalysts have
good thermal and mechanical stability and thus are ideal catalysts
for various reactions. But it involves functionalization of the carbon
or activated carbons with harmful chemicals which increase the
cost of production and is also time consuming. Hence, only a few
of them can be used on an industrial scale because of its high syn-
thetic cost (Liu et al., 2016). These shortcomings can be addressed
successfully by the use of heterogeneous catalyst derived from

https://doi.org/10.1016/j.wasman.2019.10.049
0956-053X/Ó 2019 Elsevier Ltd. All rights reserved.
 M. Gohain et al. / Waste Management 102 (2020) 212–221
biomass. Therefore, researchers began to use waste materials for
the preparation of heterogeneous catalyst from biomass: banana
peels (Lardon et al., 2009; Betiku et al., 2016), palm trunk
(Ezebor et al., 2014), wood (Sharma et al., 2012), coconut husk
(Vadery et al., 2014), egg shell (Tan et al., 2015), waste animal
bones (Nisar et al., 2017) etc. Calcined ash of some of these bio-
mass derived catalysts can be used as a catalyst without any chem-
ical functionalization for biodiesel production. However, biomass
wastes have been less explored for mixed oxide catalyst
preparation.
Therefore, a simple methodology is highly required for the
development of heterogeneous catalyst from waste biomass which
will be environmentally benign as well as cost effective. In this
work, we report the use of easily prepared catalyst from waste
i.e. littered Tectona grandis leaves for transesterification reaction.
Native to South and Southeast Asia, Tectona grandis is grown exten-
sively in India, Myanmar, Malaysia, Thailand, Sri Lanka and Bangla-
desh as its wood is highly valued for its durability and water
resistance property. It is a large, deciduous tree that occurs in
mixed hardwood forests and has large papery leaves that are often
hairy on the lower surface (Wiersema et al., 2019). Different parts
of Tectona grandis have various applications in medicinal purpose
(Nalvothula et al., 2014). Extract obtained from its leaves has been
applied for nanoparticle synthesis (Devadiga et al., 2015). But, so
far, calcined ash of this leaf has not been evaluated for the applica-
tion in organic transformations.
To evaluate the versatile nature of the catalyst, it was also
tested for knoevenagel condensation reaction (KCR) of aryl aldehy-
des containing both electron withdrawing and donating groups
with malononitrile, which are frequently applied for the produc-
tion of fine chemicals and biologically important compounds
(Tran et al., 2011; Daneshvar et al., 2018). Over the past decades,
various solid-base catalysts have been applied to this reaction,
such as zeolites exchanged with alkylammonium cations
(Martins et al., 2008), chitosan biohydrogel (Kühbeck et al.,
2012), mesoporous zirconia (Parida et al., 2010) and MOFs
(Kolmykov et al., 2016) etc. Thus, utilization of biowaste for the
preparation of heterogeneous solid-base catalyst leads to a newer
dimension with opening the scope of chemical fabrication and
knoevenagel condensation of aryl aldehydes with malononitrile.
The catalyst is renewable as well as cost effective as it is derived
from bio-waste and is prepared without any functionalization. Fur-
thermore, the recycling potentiality of the catalyst was also con-
ducted. To our best knowledge, there has not been any report on
the preparation of heterogeneous base catalyst from Tectona gran-
dis leaves for the production of biodiesel as well as KCR between
aldehydes and malononitrile (active methylene compound).
2. Materials and methods
2.1. Materials
Littered Tectona grandis leaves (TGL) were collected from the
local areas. Waste cooking oil (WO) was collected from Tezpur
University campus food court. All the chemicals were used without
further drying or purification and were purchased from Sigma
Aldrich.
2.2. Catalyst preparation and characterization
The TGL was washed thoroughly with double distilled water
and then dried under the sun. The leaves were then cut into pieces,
milled and sieved to obtain fine powder (250 lm). The sieved pow-
der was then calcined in a muffle furnace at 700 °C for 4 h to pre-
pare calcined Tectona grandis leaves (CTGL). The structural and
213
morphological characteristics of CTGL was studied by FTIR, XPS,
XRD, EDX, SEM, TEM, TGA, BET and Hammet Indicator test. The
proximate analysis of CTGL was carried out using ASTM standards.
The FTIR spectrum was recorded in Nicolet (Impact 410, USA) FTIR
spectrophotometer. XPS was recorded in Thermo Fisher Scientific
(ESCALAB Xi+) instrument. The crystalline phase of the catalyst
was evaluated using Rigaku miniflex diffractometer in a 2h range
of 20-80° with Cu Ka radiations (k = 1.5406 Å). The SEM was
recorded on an electron microscope Jeol, JSM-6290 LV and TEM
study were recorded in JEOL, JEM-2100 Plus Electron Microscope,
Japan. Elemental composition of the catalyst was determined in
Carl ZEISS Microscopy, Sigma, Germany. The thermal stability
was tested in a Model TGA-50 and DSC-60, Shimadzu under an
N2 flow rate of 1 mL/min and at 10 °C min
1 ramping rate. The sur-
face area and pore size distribution of the sample were analyzed
using NOVA 1000E, NOVA WIN, QUANTACHROME (degassing tem-
perature of 150 °C, 16 h prior to adsorption/desorption). The basic-
ity of CTGL was examined by the Hammett indicator test.
2.3. FAME production
The acid value of WO was found to be 3.73 mg KOH/g which
was not ideal for effective base-catalyzed transesterification reac-
tion. Hence, to minimize the acid value of WO to the desired acid
value of (2 mg KOH/g), the esterification step was carried out.
2.3.1. Pre-treatment of WO
Esterification was carried out in a 3-necked round bottom flask
(500 mL) equipped with a reflux condenser. A 100 mL of WO was
fed into the flask, heated to 60 °C and then cooled. To the cooled
WO, H2SO4 (1 mL) and methanol (30 mL) were added and then
continuously stirred at 800 rpm maintaining the temperature at
60 °C for 1 h. After reaction completion, it was allowed to settle
for 2 h which resulted in two distinct liquid phases. The top layer
of methanol-water was separated using a separating funnel. The
pre-treated WO layer was washed (double distilled water) and
then residuals were evaporated using rotary evaporator. The acid
value of the pre-treated WO got reduced to 1.01 mg KOH/g.
2.3.2. Transesterification reaction
The pre-treated oil was heated to 100 °C and then cooled down
to remove any traces of absorbed water. The required reaction
parameters i.e. the molar ratio of methanol, pre-treated WO and
CTGL loading were then mixed in a 3-necked glass flask reactor
(500 mL) and was equipped with a reflux condenser. The reaction
continued for the desired time maintaining the agitation speed of
650 rpm for proper mixing of methanol and oil. After completion
of the reaction, the mixture was poured into a separating funnel
wherein three layers were observed: fatty acid methyl esters, glyc-
erine and CTGL. The top layer i.e. FAME was washed with warm
distilled water (50 °C) and then evaporated using rotary evaporator
to remove any unreacted methanol to obtain WO methyl esters
(WOME).
2.4. Biodiesel analysis
The biodiesel was analyzed using 1H NMR which was recorded
in NMR spectrometer (500 MHz, Oxford, AS400, China).
The % FAME was determined using NMR technique (Gelbard
et al., 1995; Xie and Li, 2006) (CDCl3 solvent) (Eq. (1)).
2X
C MEster ð%Þ ¼  100 ð1Þ
3Y
X = Integration value of methoxy protons (-OCH3) at 3.6 ppm
Y = Integration value of a-methylene (-CH2-) protons at
2.3 ppm
214 M. Gohain et al. / Waste Management 102 (2020) 212–221
The FAME was tested by the American Society for Testing and
Material (ASTM) methods and compared with required biodiesel
standards.
2.5. Reusability of the catalyst (Biodiesel)
From an economic point of view, the reusability nature of the
catalyst is an essential factor. The recovered catalyst was washed
with hot methanol (40 °C) to remove any traces of unwanted
impurities and dried in an oven (120 °C for 3 h) (Gohain et al.,
2017) and used for successive cycles.
2.6. Knoevenagel condensation between aryl aldehydes and
malononitrile
The product formation was monitored by TLC on pre-coated
Merck silica gel plates (60F-254) and visualized under UV light. .
The isolation of desired products was achieved by column chro-
matography using silica gel (60–120 mesh). The 1H NMR spectra
were recorded on a JEOL, JNM ECS NMR spectrometer operating
at 400 MHz in CDCl3, using TMS as an internal standard. The 13C
NMR spectra were recorded at 100 MHz using CDCl3 (d = 77.00)
as standard. The structures of the purified products were con-
firmed by NMR spectra (See ESI, S1-S15).
2.6.1. Synthesis of benzylidenemalononitrile derivatives
Aryl aldehydes (0.25 mmol), malononitrile (0.5 mmol) and
CTGL (10 wt%) in ethanol (2 mL) were stirred at 60 °C for an appro-
priate period time (Table 3). After completion of the reaction (mon-
itored by TLC), the reaction mixture was centrifuged and the
catalyst was separated. The crude reaction mixture was extracted
with ethyl acetate (3  10 mL). The catalyst was washed and then
allowed to dry for further use. The resultant organic phases were
dried using Na2SO4 (anhydrous), evaporated under reduced pres-
sure, and then purified by column chromatography using ethyl
acetate and hexane (1:5; v/v) as an eluent.
2.7. Reusability of the catalyst (Knoevenagel Condensation)
The recyclability of CTGL towards KCR of aldehydes was tested
using the model reaction of chlorobenzaldehyde and malononitrile
under same optimal condition. After 1st cycle, the catalyst was fil-
tered and washed several times with ethyl acetate followed by
H2O. The recovered catalyst was dried in oven at 100 °C for over-
night and was further used for the consecutive runs.
Fig. 1. (a) XRD pattern and (b) FTIR spectra of CTGL.
3. Results and discussion
With the concept of environmental sustainability many atten-
tions have been given in utilization of biowaste for the synthesis
of fuels and chemicals in order to reduce the use of hazardous
chemicals. Thus, in present protocol we use CTGL an agro-waste
as a renewable catalyst for chemical transformation.
3.1. CTGL characterization
The XRD analysis of CTGL [Fig. 1(a)] revealed the presence of
metal oxides and carbonates in abundance. Strong characteristic
peaks of K2O and K2CO3 were seen at 2h = 25.28, 26.59, 28.41,
31.4, 40.55, 44 (JCPDS reference code 00-026-1327, 00-16-820,
77-2176, 85-514, 87-0730). The peaks at 2h = 30.01, 39, 43, 47,
52.50 (JCPDS reference code 16-820, 87-1863, 82-1691, 01-085-
0514) revealed the presence of CaO and CaCO3 in the CTGL. Previ-
ous literatures also reported the presence of CaO in their catalyst
comparable 2h values (Wilson et al., 2008; Pathak et al., 2018;
Laskar et al., 2018; Zhao et al., 2018). The peaks at 2h = 34.13 con-
firmed the presence of SiO2 (JCPDS reference code 89-3609, 89-
7746) (Wang et al., 2017). It was found that CTGL contains oxides
of K and Ca which have very strong basic sites. The group I alkali
metal hydroxide and group II metal oxide exhibits good transester-
ification activity due to their higher basicity.
The functional groups present in CTGL were analyzed by FTIR
[Fig. 1(b)]. The broad peak at 3400 cm
1 [Fig. 1(b)] is associated
with OAH stretching (Betiku et al., 2016), which is due to absorbed
water molecules on the surface of CTGL. The bands at 2320 cm
1
and 2175 cm
1 are attributed to the SiAOAK, MgAOAK bonds
stretching vibrations. The SiAOASi bonds peak was observed at
1000 cm
1 which further supports the XRD peak of SiO2 compo-
nent [Fig. 1(a)]. The characteristic peak at 560 cm
1 is due to
stretching vibrations of CaAO and KAO (Liu et al., 2016; Stork
and Pott, 1974). The peaks at 1654 cm
1, 1389 cm
1, 870 cm
1
and 700 cm
1 are attributed to CAO bond of metal carbonates that
may be formed due to CO2 absorption on to the surface of metal
oxides of CTGL which detects the presence of K, Ca and metal car-
bonates (Sharma et al., 2012). Similar type of bands for carbonates
was also reported for some of the earlier reported ash catalysts
(Betiku et al., 2016; Gohain et al., 2017). Therefore, the predictions
concurred in the FT-IR study of CTGL confirms the presence of car-
bonate and oxide of metals in the catalyst and is consistent with
the XRD analysis.
EDX study supported the FTIR and XRD data and elucidates the
chemical nature of CTGL. The EDX (ESI, S16) analysis confirmed the
 M. Gohain et al. / Waste Management 102 (2020) 212–221
Fig. 2. XPS spectra of CTGL (a) O 1s, (b) K 2p and (c) Ca 2p.
presence of K (53.25 wt%), Ca (30.28 wt%), Si (10.03 wt%), Mg
(4.77 wt%) and Na (1.67 wt%). The proximate analysis of CTGL is
shown in ESI, S16.
The XPS analysis supported the findings of EDX, and showed
peaks for K, Ca, Mg, Si and Na. The peak observed at 529.06 eV
and 531.84 eV in O 1s spectra [Fig. 2(a)] can be attributed to metal
oxides and metal carbonates respectively. Peaks appeared at bind-
ing energy 292.5 eV and 295 eV in K 2p spectra [Fig. 2(b)] denotes
the presence of potassium in the form of oxides or carbonates
(Pathak et al., 2018). The peaks at 346.48 eV and 350 eV in Ca 2p
spectra [Fig. 2(c)] denote the presence of Ca in oxides form
(Nefedov et al., 1974). These results strongly suggest that both
strong and moderately basic sites are present on CTGL.
From observed results, K was found to be the major ingredient
in CTGL and K2O being a strong base resulting strong basicity of
CTGL. Strong bases can remove protons from methanol and
develop active methoxy species which are responsible for efficient
transesterification (Gohain et al., 2017).
To assess the thermal stability and behavior of CTGL, TG analy-
sis (ESI, S16) was performed at elevated temperature upto 700 °C.
A total of 9% weight loss in CTGL was observed. The loss of surface
water present in CTGL was observed until 380.72 °C. Another slight
loss from 380.72 °C to 450 °C is attributed to inorganic impurities
present in CTGL. At 450 °C oxidation of carbonaceous material
and release of CO, CO2 etc (Chouhan and Sarma, 2013) started
and continued upto 660 °C, beyond which no further weight loss
was observed.
Both the SEM and TEM [Fig. 3(a) and (b)] analysis revealed
mesoporous and microporous nature of CTGL which indicates large
215
surface area and high porosity. Higher surface area enhances inter-
action between active sites and reactants of the catalysts (Gohain
et al., 2017). The microporous nature of CTGL will provide an ade-
quate external surface which will act as active sites for rapid mass
transfer for the transesterification process (Wang et al., 2017).
BET study was performed to measure the surface area, pore vol-
ume and pore size of CTGL which was found to be 116.833 m2 g
1,
0.185 cm3 g
1 and 112.210 Å respectively. The N2 physisorption of
CTGL exhibits type-IV isotherm revealing its mesoporous charac-
teristic (ESI, S17). Deka and Basumatary (2011), Wang et al.
(2017), Pathak et al. (2018) reported the surface area as 1.487 m2
g
1, 1.266 m2 g
1, 4.442 m2 g
1, 1.4546 m2 g
1 respectively, which
are much lower compared to the present catalyst i.e. CTGL
(116.833 m2 g
1). They showed lower catalytic ability which is
probably due to their lower surface area as increase in the surface
area increases the catalytic activity.
The basic strength of CTGL was found to be 9.8 < H  18.4 using
Hammett indicator test. After calcination TGL the metal carbonate
salts gets thermally activated to active metal oxide (Lee et al.,
2014). According to reported literature, potassium leaching can
be prevented by calcination, and hence may increase the catalyst
reusability (Sharma et al., 2012).
3.2. Biodiesel characterization
Fig. 4(a) and (b) show the 1H NMR spectra of WO and WOME
respectively. A singlet appeared at d 3.6 due to the methoxy group
and a triplet at d 2.3 corresponding to a-CH2 protons [Fig. 4(b)]
which is the major differences in signals compared to WO [Fig. 4
216 M. Gohain et al. / Waste Management 102 (2020) 212–221
Fig. 3. (a) SEM image and (b) TEM image of CTGL.
(a)] confirms the formation of biodiesel. Other peaks appeared at d
0.85, d 1.2 and a multiplet at d 1.6 are assigned to terminal methyl
protons, methylene protons and b-carbonyl methylene protons
respectively. The peak at d 5.3 is due to olefinic hydrogens (Tariq
et al., 2011; Diehl and Randel, 2007; Monteiro et al., 2009). The dis-
appearance of glycerol moiety signals at d 4.1–4.4 in Fig. 4(b),
clearly showed the conversion of WO to FAME.
Using Eq. (1), 100% FAME conversion was found with a 6:1 M
ratio of methanol/oil, 2.5 wt% CTGL loading within 3 h. The physic-
ochemical properties of pre-treated WO are shown in ESI, S17. The
WOME fuel properties (Table 1) meet the biodiesel standards
(ASTM D 6751 and EN 14214).
3.3. Influence of reaction parameters on biodiesel production
3.3.1. Catalyst loading
The influence of catalyst loading on biodiesel conversion was
analyzed by changing catalyst loadings (CTGL) from 0.5 to 4.5 wt
% [Fig. 5(a)] using a 6:1 M ratio of methanol/oil and performing
the reaction at room temperature. The low conversion was
achieved at lower catalyst loading due to availability of lesser basic
sites which is required for conversion of oil to FAME. It was
observed that FAME conversion increased with higher catalyst
loading, due to an increase in the active sites which favors the con-
tact time of reactants and catalysts (Olutoye et al., 2011). But it was
observed that with further increase in catalyst amount FAME con-
version got reduced. This may be due to the lower diffusion of the
reaction mixtures (catalyst, methanol and oil) in higher catalyst
amount (Mansir et al., 2018). The three phase solution becomes
more viscous with higher catalyst loading which could resist the
mass transfer among the reactants and saponification reaction
for base catalyzed reactions may get induce that decreased the
FAME conversion (Kaur and Ali, 2014; Meher et al., 2006).
3.3.2. Molar ratio of methanol/oil
The influence of methanol/oil molar ratio was also studied
[Fig. 5(b)]. Transesterification reaction was performed with 2:1,
4:1, 6:1, 8:1 and 10:1 methanol/oil molar ratio for 3 h using
2.5 wt% CTGL loading. As there was less contact between the cata-
lyst and the reactants, FAME conversion decreases at lower metha-
nol/oil molar ratio. Transesterification being a reversible reaction,
excess methanol is vital to shift the reaction in direction of the
products (Olutoye et al., 2011). With an increase in the molar ratio
of methanol/oil FAME conversion got increased owing to the for-
mation of methoxy species on catalyst surface which shifted the
reaction towards the forward direction. But a decrease in the con-
version of FAME was also observed with further increase in metha-
nol/oil molar ratio as higher methanol/oil molar ratio leads to
reverse reaction that reduces the FAME conversion (Ma and
Hanna, 1999; Xie and Huang, 2006).
3.3.3. Reaction time
Fig. 5(c) shows the influence of time on FAME conversion exam-
ined by varying the time from 1 h to 5 h, using 6:1 M ratio of
methanol/oil and 2.5 wt% of CTGL loading. Conversion of FAME
was low at the first 1 h because of slow dispersion of triglycerides
into the methanol phase. However, with further increase in reac-
tion time, FAME conversion got increased gradually until the reac-
tion attains the equilibrium (Vyas et al., 2009). Long reaction time
may drive the reaction backward resulting in lower FAME conver-
sion (Wan et al., 2014) after 5 h.
The plausible mechanism for transesterification of triglyceride
to biodiesel using CTGL as a heterogeneous base catalyst is shown
in Scheme 1. It is assumed that initially the basic sites present in
CTGL abstract the proton from methanol to give methoxide. This
methoxide then react with carbonyl group present in triglyceride
to give biodiesel and at the same time catalyst is recovered to be
used for next cycles.
3.3.4. Catalyst deactivation and reusability potency (Biodiesel)
Recyclability of a catalyst is an important characteristic from
the point of green chemistry (Ferré et al., 2016). Methanol/oil
molar ratio of 6:1, catalyst loading of 2.5 wt% and room tempera-
ture were selected as the optimized reaction parameters [Fig. 5
(d)]. It was found that on reusing CTGL, biodiesel conversion got
reduced with each successive cycle. This lower FAME conversion
may be attributed to the leaching of the catalyst which resulted
in a reduction of active sites of the catalyst (Long et al., 2014).
The K and Ca have a greater tendency of getting leached into the
solution more readily than other elements (Wang et al., 2017).
Hence, K leaching may be one of the main reasons for catalyst
deactivation due to considerable solubility of K2O in methanol
and glycerol. Another reason may be the loss of catalyst amount
during washing and transfer between cycles.
The FTIR analysis showed that upon repeated use of CTGL glyc-
erol and ester got agglomerated on it (ESI, S17) which may result in
blockage of active sites leading to lower FAME conversion. This was
evident by the appearance of a band at 1750 cm
1 which indicates
adsorbed esters. The intensity of the peaks at 1389 cm
1 and
1000 cm
1 got reduced in the reused CTGL which signifies the loss
of K and Si resulting in the availability of lower basic sites. The
bands at 1050 cm
1 and 2800 cm
1 exhibits ACAO (primary alco-
hol) and CAH stretching indicating Ca(OCH3)2 formation due to the
reaction of methanol and glycerine with CaO onto the surface of
CTGL. The Ca(OCH3)2 and absorbed esters resulted in pores block-
age which lowered the mass transfer during the reaction results in
lowering FAME conversion (Kawashima et al., 2009). TEM and XRD
analyses of recovered CTGL were also investigated. The TEM anal-
 M. Gohain et al. / Waste Management 102 (2020) 212–221 217

1.0 W O.001.esp

0.9
(a)
0.8

0.7
Normalized Intensity

0.6

0.5

0.4

0.3

0.2

0.1

8 7 6 5 4 3 2 1 0 -1
Chemical Shif t (ppm)

1.0 W OME 1H.001.esp

0.9
(b)
0.8

0.7

0.6
Normalized Intensity

0.5

0.4

0.3

0.2

0.1

0
0.00 0.09 0.09 0.04 0.06 0.11 0.07 0.55 0.01 0.09 0.00

8 7 6 5 4 3 2 1 0 -1
Chemical Shif t (ppm)

Fig. 4. 1H NMR spectra of (a) WO and (b) WOME.

Table 1
Fuel properties of WOME.

Fuel Property Unit Biodiesel ASTM D 6751 EN 14214

Acid Number mg KOH per g 0.07 <0.80 0.5 max
Viscosity at 40 °C mm2 per sec 4.15 1.9–6.0 3.5–5.0
Density at 15 °C g per cc 0.85 0.86–0.90 0.85
Carbon residue % wt. 0.016 0.050 max 0.3
Calorific value MJ per kg 39.32 – 35 min
Cetane Number 58 47 min 51 min
Cloud point °C
5 – –
Pour point °C
9 – –
Flash point °C 148 93 min 120 min
218 M. Gohain et al. / Waste Management 102 (2020) 212–221
Fig. 5. Influence of (a) CTGL loading, (b) Methanol/oil molar ratio, (c) time and (d) reusability on FAME conversion.
ysis of the reused CTGL (ESI, S18) supported the FTIR findings and
depicted less porous nature of reused CTGL. The XRD analysis of
the recycled CTGL catalyst exhibited a sharp decrease in the inten-
sity of potassium oxide, the major basic site of CTGL (ESI, S18).
Hence, pore blockage and reduction in the basic sites on reusing
the catalyst might have resulted in lower FAME conversion.
3.4. Optimization of reaction condition for Knoevenagel condensation
Table 2 well illustrated the optimization process for the amount
of substrate, solvent effect, catalyst loading and period time. The
efficiency CTGL was initially assessed in the reaction of 4-
Chlorobenzaldehyde (0.25 mmol), and malononitrile (0.5 mmol)
using different solvents at 60 °C. The process aimed to provide
the absolute formation of benzylidenemalononitrile (BMN) deriva-
tives at 60 °C. Various reports (Göksu and Gültekin, 2017; Ding
et al., 2015; Sakthivel and Dhakshinamoorthy, 2017) suggests the
production of BMN, but the longer period time and efficient pro-
duct formation always a challenging task. To overcome this, the
present protocol is based on the successful completion of KCR
remarkably with high yield in short reaction period and catalyst
reusability. Eventually, 0.5 mmol of 4-Chlorobenzaldehyde,
1.0 mmol of malononitrile and 2.0 mg of catalyst provide sufficient
concert for knoevenagel condensation in 2 mL of ethanol (Table 2,
entry 9). At the same time, the desired product formation took 3 h
in trace amounts with no use of catalyst (Table 2, entry 10) signi-
fying the excellent catalytic activity of CTGL for KCR.
Moreover, Table 3 summarizes the successful conversion of all
aryl aldehyde derivatives to BMN derivatives in the presence of
CTGL catalyst. The BMN derivatives were obtained in high yields
using minimum solvent for a shorter period (10–30 min) of time
at 60 °C. Considering the high catalytic efficiency of CTGL towards
malononitrile and 4-Chlorobenzaldehyde, different benzaldehyde
derivatives were chosen as reaction substrates. For Knoevenagel
condensation, nucleophilic addition is a rate-determining step,
thus electron-withdrawing groups are more reactive than those
of electron-donating groups (Bhunia et al., 2016) in BMN deriva-
tives formation. Table 3, clearly showed the derivatives of ben-
zaldehyde having electron-withdrawing groups (ANO2, ACN, ACl
etc) showed more conversion to catalytic products to those of
electron-donating benzaldehyde derivatives (ACH3, AOH, AOMe).
Compounds 21 and 29 were successfully synthesized but in low
yields. 3,4,5-Trimethoxybenzaldehyde (entry 9), showed low yield
to the desired product is plausibly due to the sterical hindrance of
three methoxy groups along with the electron-donating effect.
Thus, to obtain the catalytic yields, the substituents of benzalde-
hyde play a major role in the reaction of aldehydes with
malononitrile.
A plausible mechanistic pathway for Knoevenagel condensation
catalyzed by CTGL has been proposed in Scheme 1.
 M. Gohain et al. / Waste Management 102 (2020) 212–221 219

Scheme 1. Plausible mechanism for transesterification of triglycerides to biodiesel and Knoevenagel condensation catalyzed by CTGL base catalyst.

Table 2 Table 3
Optimization conditions for KCR of 4-Cl-benzaldehyde with malononitrile.a KCR of aryl aldehyde derivatives with malononitrile in presence of CTGL catalyst.a

Sl. No. Solvent CTGL (mg) Time (min) Yield (%)b Sl. No. Substrate Product Time (min) Yield (%)b
1 H2O 2 120 Trace 1 12 94
2 MeOH 2 120 60 2 10 95
3 CH2Cl2 2 120 Trace 3 10 96
4 CH3CN 2 120 Trace 4 14 91
5 MeOH/H2O (2:1) 2 60 40 5 25 90
6 WEB 2 60 55 6 15 87
7 WEB/EtOH (2:1) 2 30 80 7 16 86
8 WEB/EtOH (2:2) 2 25 85 8 16 86
9 EtOH 2 10 95 9 22 84
10 EtOH – 180 Trace 10 20 86
a 11 30 81
Reaction condition: Chlorobenzaldehyde (0.25 mmol), malononitrile
12 14 93
(0.5 mmol), CTGL (10 wt% of substrate) at 60 °C.
b 13 11 97
Isolated yields.
14 10 96
15 17 86
16 12 92
17 14 91
3.4.1. Catalyst reusability potency (Knoevenagel condensation) 18 15 91
For KCR, the catalyst was used five times and it was found that 19 18 85
the catalyst maintained good activity for a minimum of five con- a
Reaction condition: Aldehydes (0.25 mmol), malononitrile (0.5 mmol), CTGL
secutive cycles demonstrating the catalyst can be reused without (10 wt% of substrate) at 60 °C.
b
a significant reduction in the yield (ESI, S18). Isolated yields.
220 M. Gohain et al. / Waste Management 102 (2020) 212–221
4. Conclusion
We described a bio-refinery approach wherein the application
of CTGL having multifunctional use, capable of producing fuel as
well as chemical as a renewable, reusable and low cost heteroge-
neous base catalyst. Considering the simplicity in catalyst prepara-
tion which does not involve any chemical treatment or
functionalization makes our catalyst environmentally benign.
FAME conversion of 100% was achieved at room temperature using
2.5 wt% catalyst loading and 6: 1 methanol/oil molar ratio. For KCR,
CTGL catalyst showed a promising catalytic activity towards the
formation of BMN derivatives of aryl aldehydes. The widespread
scope, reusability of catalyst, improved reaction rate and yield of
the product are the advantages of the present protocol.
Declaration of Competing 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 and IIT Guwahati for assisting
in performing analyses.
Appendix A. Supplementary material
Supplementary data to this article can be found online at
https://doi.org/10.1016/j.wasman.2019.10.049.
References
Agarwal, S., Singhal, S., Singh, M., Arora, S., Tanwer, M., 2018. Role of antioxidants in
enhancing oxidation stability of biodiesels. ACS Sustain. Chem. Eng. 6, 11036–
11049. https://doi.org/10.1021/acssuschemeng.8b02523.
Ajala, O.E., Aberuagba, F., Odetoye, T.E., Ajala, A.M., 2015. Biodiesel: sustainable
energy replacement to petroleum-based diesel fuel–A review. ChemBioEng Rev.
2, 145–156. https://doi.org/10.1002/cben.201400024.
Betiku, E., Akintunde, A.M., Ojumu, T.V., 2016. Banana peels as a biobase catalyst for
fatty acid methyl esters production using Napoleon’s plume (Bauhinia
monandra) seed oil: A process parameters optimization study. Energy 103,
797–806. https://doi.org/10.1016/j.energy.2016.02.138.
Bhunia, A., Dey, S., Moreno, J.M., Diaz, U., Concepcion, P., Van Hecke, K., Janiak, C.,
Van Der Voort, P., 2016. A homochiral vanadium–salen based cadmium bpdc
MOF with permanent porosity as an asymmetric catalyst in solvent-free
cyanosilylation. Chem. Commun. 52, 1401–1404. https://doi.org/10.1039/
C5CC09459C.
Chouhan, A.P.S., Sarma, A.K., 2013. Biodiesel production from Jatropha curcas L. oil
using Lemna perpusilla Torrey ash as heterogeneous catalyst. Biomass
Bioenergy 55, 386–389. https://doi.org/10.1016/j.biombioe.2013.02.009.
Daneshvar, N., Shirini, F., Langarudi, M.S.N., Karimi-Chayjani, R., 2018. Taurine as a
green bio-organic catalyst for the preparation of bio-active barbituric and
thiobarbituric acid derivatives in water media. Bioorganic Chem. 77, 68–73.
https://doi.org/10.1016/j.bioorg.2017.12.021.
Deka, D.C., Basumatary, S., 2011. High quality biodiesel from yellow oleander
(Thevetia peruviana) seed oil. Biomass Bioenergy 35, 1797–1803. https://doi.
org/10.1016/j.biombioe.2011.01.007.
Devadiga, A., Shetty, K.V., Saidutta, M.B., 2015. Timber industry waste-teak (Tectona
grandis Linn.) leaf extract mediated synthesis of antibacterial silver
nanoparticles. International. Nano Lett. 5, 205–214. https://doi.org/10.1007/
s40089-015-0157-4.
Diehl, B., Randel, G., 2007. Analysis of biodiesel, diesel and gasoline by NMR
spectroscopy–a quick and robust alternative to NIR and GC. Lipid Technol. 19,
258–260. https://doi.org/10.1002/lite.200700087.
Ding, Y., Ni, X., Gu, M., Li, S., Huang, H., Hu, Y., 2015. Knoevenagel condensation of
aromatic aldehydes with active methylene compounds catalyzed by lipoprotein
lipase. Catal. Commun. 64, 101–104. https://doi.org/10.1016/
j.catcom.2015.02.007.
Ezebor, F., Khairuddean, M., Abdullah, A.Z., Boey, P.L., 2014. Oil palm trunk and
sugarcane bagasse derived heterogeneous acid catalysts for production of fatty
acid methyl esters. Energy 70, 493–503. https://doi.org/10.1016/j.
energy.2014.04.024.
Ferré, M., Pleixats, R., Man, M.W.C., Cattoën, X., 2016. Recyclable organocatalysts
based on hybrid silicas. Green Chem. 18, 881–922. https://doi.org/10.1039/
C5GC02579F.
Gelbard, G., Bres, O., Vargas, R.M., Vielfaure, F., Schuchardt, U.F., 1995. 1H nuclear
magnetic resonance determination of the yield of the transesterification of
rapeseed oil with methanol. J. Am. Oil. Chem. Soc. 72, 1239–1241. https://doi.
org/10.1007/BF02540998.
Gohain, M., Devi, A., Deka, D., 2017. D, Musa balbisiana Colla peel as highly effective
renewable heterogeneous base catalyst for biodiesel production. Ind. Crops
Prod. 109, 8–18. https://doi.org/10.1016/j.indcrop.2017.08.006.
Gohain, M., Laskar, K., Paul, A.K., Daimary, N., Maharana, M., Goswami, I.K.,
Hazarika, A., Bora, U., Deka, D., 2019. Carica papaya stem: A source of versatile
heterogeneous catalyst for biodiesel production and C-C bond formation.
Renew. Energy 147, 541–555. https://doi.org/10.1016/j.renene.2019.09.016.
Göksu, H., Gültekin, E., 2017. Pd nanoparticin aluminium oxy-hydroxide: an
efficient and recyclable heterogeneous catalyst for selective knoevenagel
condensatles incarcerated ion. ChemistrySelect 2, 458–463. https://doi.org/
10.1002/slct.201601721.
Janaun, J., Ellis, N., 2010. Perspectives on biodiesel as a sustainable fuel. Renew. Sust.
Energ. Rev. 14, 1312–1320. https://doi.org/10.1016/j.rser.2009.12.011.
Kaur, N., Ali, A., 2014. Kinetics and reusability of Zr/CaO as heterogeneous catalyst
for the ethanolysis and methanolysis of Jatropha crucas oil. Fuel Process.
Technol. 119, 173–184. https://doi.org/10.1016/j.fuproc.2013.11.002.
Kawashima, A., Matsubara, K., Honda, K., 2009. Acceleration of catalytic activity of
calcium oxide for biodiesel production. Bioresour. Technol. 100, 696–700.
https://doi.org/10.1016/j.biortech.2008.06.049.
Kolmykov, O., Chebbat, N., Commenge, J.M., Medjahdi, G., Schneider, R., 2016. ZIF-8
nanoparticles as an efficient and reusable catalyst for the Knoevenagel
synthesis of cyanoacrylates and 3-cyanocoumarins. Tetrahedron Lett. 57,
5885–5888. https://doi.org/10.1016/j.tetlet.2016.11.070.
Konwar, L.J., Das, R., Thakur, A.J., Salminen, E., Mäki-Arvela, P., Kumar, N., Mikkola, J.
P., Deka, D., 2014. Biodiesel production from acid oils using sulfonated carbon
catalyst derived from oil-cake waste. J. Mol. Catal. A 388, 167–176. https://doi.
org/10.1016/j.molcata.2013.09.031.
Kühbeck, D., Saidulu, G., Reddy, K.R., Díaz, D.D., 2012. Critical assessment of the
efficiency of chitosan biohydrogel beads as recyclable and heterogeneous
organocatalyst for C-C bond formation. Green Chem. 14, 378–392. https://doi.
org/10.1039/C1GC15925A.
Lardon, L., Helias, A., Sialve, B., Steyer, J.P., Bernard, O., 2009. Life-cycle assessment
of biodiesel production from microalgae. Environ. Sci. Technol. 43, 6475–6481.
https://doi.org/10.1021/es900705j.
Laskar, I.B., Rajkumari, K., Gupta, R., Chatterjee, S., Paul, B., Rokhum, L., 2018. Waste
snail shell derived heterogeneous catalyst for biodiesel production by the
transesterification of soybean oil. RSC Adv. 8, 20131–20142. https://doi.org/
10.1039/C8RA02397B.
Lee, A.F., Bennett, J.A., Manayil, J.C., Wilson, K., 2014. Heterogeneous catalysis for
sustainable biodiesel production via esterification and transesterification.
Chem. Soc. Rev. 43, 7887–7916. https://doi.org/10.1039/C4CS00189C.
Li, J., Guo, Z., 2017. Catalytic biodiesel production mediated by amino acid-based
protic salts. ChemSusChem 10, 1792–1802. https://doi.org/10.1002/
cssc.201700026.
Liu, H., Shuang Guo, H., Jing Wang, X., Zhong Jiang, J., Lin, H., Han, S., Peng Pei, S.,
2016. Mixed and ground KBr-impregnated calcined snail shell and kaolin as
solid base catalysts for biodiesel production. Renew. Energ. 93, 648–657.
https://doi.org/10.1016/j.renene.2016.03.017.
Liu, X., He, H., Wang, Y., Zhu, S., 2007. Transesterification of soybean oil to biodiesel
using SrO as a solid base catalyst. Catal. Commun. 8, 1107–1111. https://doi.
org/10.1016/j.catcom.2006.10.026.
Long, Y.D., Fang, Z., Su, T.C., Yang, Q., 2014. Co-production of biodiesel and hydrogen
from rapeseed and Jatropha oils with sodium silicate and Ni catalysts. Appl.
Energy 113, 1819–1825. https://doi.org/10.1016/j.apenergy.2012.12.076.
Ma, F., Hanna, M.A., 1999. Biodiesel production: a review. Bioresour. Technol. 70, 1–
15. https://doi.org/10.1016/S0960-8524(99)00025-5.
Mansir, N., Teo, S.H., Rabiu, I., Taufiq-Yap, Y.H., 2018. Effective biodiesel synthesis
from waste cooking oil and biomass residue solid green catalyst. Chem. Eng. J.
347, 137–144. https://doi.org/10.1016/j.cej.2018.04.034.
Martins, L., Vieira, K.M., Rios, L.M., Cardoso, D., 2008. Basic catalyzed Knoevenagel
condensation by FAU zeolites exchanged with alkylammonium cations. Catal.
Today 133, 706–710. https://doi.org/10.1016/j.cattod.2007.12.043.
Meher, L.C., Sagar, D.V., Naik, S.N., 2006. Technical aspects of biodiesel production
by transesterification-a review. Renew. Sust. Energ. Rev. 10, 248–268. https://
doi.org/10.1016/j.rser.2004.09.002.
Monteiro, M.R., Ambrozin, A.R.P., Liao, L.M., Ferreira, A.G., 2009. Determination of
biodiesel blend levels in different diesel samples by 1H NMR. Fuel 88, 691–696.
https://doi.org/10.1016/j.fuel.2008.10.010.
Nalvothula, R., Nagati, V.B., Koyyati, R., Merugu, R., Padigya, P.R.M., 2014. Biogenic
synthesis of silver nanoparticles using Tectona grandis leaf extract and
evaluation of their antibacterial potential. Int. J. Chem. Tech. Res. 6, 293–298
http://sphinxsai.com/2014/ChemTech/JM14CT1_50/CT=34(293-298)JM14.pdf.
Nefedov, V.I., Buslaev, Y.A., Kokunov, Y.V., 1974. X-ray electron spectroscopy of
alkali metal fluorides and alkaline earth metal fluorides. Zh. Neorg. Khim. 19,
1166–1169 https://inis.iaea.org/search/search.aspx?orig_q=RN:6162099.
Nisar, J., Razaq, R., Farooq, M., Iqbal, M., Khan, R.A., Sayed, M., Shah, A., ur Rahman, I.,
2017. Enhanced biodiesel production from Jatropha oil using calcined waste
animal bones as catalyst. Renew. Energ. 101, 111–119. https://doi.org/10.1016/
j.renene.2016.08.048.
 M. Gohain et al. / Waste Management 102 (2020) 212–221
Noureddini, H., Zhu, D., 1997. Kinetics of transesterification of soybean oil. J.
Am. Oil. Chem. Soc. 74, 1457–1463. https://doi.org/10.1007/s11746-997-
0254-2.
Olutoye, M.A., Lee, S.C., Hameed, B.H., 2011. Synthesis of fatty acid methyl ester
from palm oil (Elaeis guineensis) with Ky (MgCa)2xO3 as heterogeneous
catalyst. Bioresour. Technol. 102, 10777–10783. https://doi.org/10.1016/j.
biortech.2011.09.033.
Parida, K.M., Mallick, S., Sahoo, P.C., Rana, S.K., 2010. A facile method for synthesis of
amine-functionalized mesoporous zirconia and its catalytic evaluation in
Knoevenagel condensation. Appl. Catal. A. 381, 226–232. https://doi.org/
10.1016/j.apcata.2010.04.008.
Pathak, G., Das, D., Rajkumari, K., Rokhum, L., 2018. Exploiting waste: towards a
sustainable production of biodiesel using Musa acuminata peel ash as a
heterogeneous catalyst. Green Chem. 20, 2365–2373. https://doi.org/10.1039/
C8GC00071A.
Piker, A., Tabah, B., Perkas, N., Gedanken, A., 2016. A green and low-cost room
temperature biodiesel production method from waste oil using egg shells as
catalyst. Fuel 182, 34–41. https://doi.org/10.1016/j.fuel.2016.05.078.
Rafiei, S., Tangestaninejad, S., Horcajada, P., Moghadam, M., Mirkhani, V.,
Mohammadpoor-Baltork, I., Kardanpour, R., Zadehahmadi, F., 2018. Efficient
biodiesel production using a lipase@ ZIF-67 nanobioreactor. Chem. Eng. J. 334,
1233–1241. https://doi.org/10.1016/j.cej.2017.10.094.
Roschat, W., Siritanon, T., Yoosuk, B., Promarak, V., 2016. Rice husk-derived sodium
silicate as a highly efficient and low-cost basic heterogeneous catalyst for
biodiesel production. Energy Convers. Manag. 119, 453–462. https://doi.org/
10.1016/j.enconman.2016.04.071.
Sakthivel, B., Dhakshinamoorthy, A., 2017. Chitosan as a reusable solid base catalyst
for Knoevenagel condensation reaction. J. Colloid. Interface. Sci. 485, 75–80.
https://doi.org/10.1016/j.jcis.2016.09.020.
Sano, N., Yamada, K., Tsunauchi, S., Tamon, H., 2017. A novel solid base catalyst for
transesterification of triglycerides toward biodiesel production: Carbon
nanohorn dispersed with calcium ferrite. Chem. Eng. J. 307, 135–142. https://
doi.org/10.1016/j.cej.2016.08.010.
Sharma, M., Khan, A.A., Puri, S.K., Tuli, D.K., 2012. Wood ash as a potential
heterogeneous catalyst for biodiesel synthesis. Biomass Bioenergy 41, 94–106.
https://doi.org/10.1016/j.biombioe.2012.02.017.
Sharma, Y.C., Singh, B., Korstad, J., 2009. High yield and conversion of biodiesel from
a nonedible feedstock (Pongamia pinnata). J. Agric. Food Chem. 58, 242–247.
https://doi.org/10.1021/jf903227e.
Steen, E.J., Kang, Y., Bokinsky, G., Hu, Z., Schirmer, A., McClure, A., Cardayre, S.B.,
Keasling, J.D., 2010. Microbial production of fatty-acid-derived fuels and
chemicals from plant biomass. Nature 463, 559. https://doi.org/
10.1038/nature08721.
Stork, W.H.J., Pott, G.T., 1974. Studies of compound formation on alkali/gamma.-
aluminum oxide catalyst systems using chromium, iron, and manganese
luminescence. J. Phys. Chem. 78, 2496–2506 https://pubs.acs.org/doi/pdf/10.
1021/j100617a016.
Tan, Y.H., Abdullah, M.O., Nolasco-Hipolito, C., Taufiq-Yap, Y.H., 2015. Waste
ostrich-and chicken-eggshells as heterogeneous base catalyst for biodiesel
production from used cooking oil: Catalyst characterization and biodiesel yield
performance. Appl. Energy 160, 58–70. https://doi.org/10.1016/j.
apenergy.2015.09.023.
Tan, Y.H., Abdullah, M.O., Kansedo, J., Mubarak, N.M., San Chan, Y., Nolasco-Hipolito,
C., 2019. Biodiesel production from used cooking oil using green solid catalyst
derived from calcined fusion waste chicken and fish bones. Renew. Energy 139,
696–706. https://doi.org/10.1016/j.renene.2019.02.110.
221
Tang, S., Wang, L., Zhang, Y., Li, S., Tian, S., Wang, S.B., 2012. Study on preparation of
Ca/Al/Fe3O4 magnetic composite solid catalyst and its application in biodiesel
transesterification. Fuel Process. Technol. 95, 84–89. https://doi.org/10.1016/
j.fuproc.2011.11.022.
Tariq, M., Ali, S., Ahmad, F., Ahmad, M., Zafar, M., Khalid, N., Khan, M.A., 2011.
Identification, FT-IR, NMR (1H and 13C) and GC/MS studies of fatty acid methyl
esters in biodiesel from rocket seed oil. Fuel Process. Technol. 92, 336–341.
https://doi.org/10.1016/j.fuproc.2010.09.025.
Teo, S.H., Islam, A., Ng, C.H., Mansir, N., Ma, T., Thomas Choong, S.Y., Taufiq-Yap, Y.
H., 2018. Methoxy-functionalized mesostructured stable carbon catalysts for
effective biodiesel production from non-edible feedstock. Chem. Eng. J. 334,
1851–1868. https://doi.org/10.1016/j.cej.2017.11.110.
Toda, M., Takagaki, A., Okamura, M., Kondo, J.N., Hayashi, S., Domen, K., Hara, M.,
2005. Green chemistry: biodiesel made with sugar catalyst. Nature 438, 178.
https://doi.org/10.1038/438178a.
Tran, U.P.N., Le, K.K.A., Phan, N.T.S., 2011. Expanding applications of metal
organic
frameworks: zeolite imidazolate framework ZIF-8 as an efficient heterogeneous
catalyst for the knoevenagel reaction. ACS Catal. 1, 120–127. https://doi.org/
10.1021/cs1000625.
Vadery, V., Narayanan, B.N., Ramakrishnan, R.M., Cherikkallinmel, S.K., Sugunan, S.,
Narayanan, D.P., Sasidharan, S., 2014. Room temperature production of jatropha
biodiesel over coconut husk ash. Energy 70, 588–594. https://doi.org/10.1016/j.
energy.2014.04.045.
Vyas, A.P., Subrahmanyam, N., Patel, P.A., 2009. Production of biodiesel through
transesterification of Jatropha oil using KNO3/Al2O3 solid catalyst. Fuel 88, 625–
628. https://doi.org/10.1016/j.fuel.2008.10.033.
Wan, L., Liu, H., Skala, D., 2014. Biodiesel production from soybean oil in subcritical
methanol using MnCO3/ZnO as catalyst. Appl. Catal. B. 152, 352–359. https://
doi.org/10.1016/j.apcatb.2014.01.033.
Wang, J., Xing, S., Huang, Y., Fan, P., Fu, J., Yang, G., Yang, L., Lv, P., 2017a. Highly
stable gasified straw slag as a novel solid base catalyst for the effective
synthesis of biodiesel: Characteristics and performance. Appl. Energy 190, 703–
712. https://doi.org/10.1016/j.apenergy.2017.01.004.
Wang, S., Zhao, C., Shan, R., Wang, Y., Yuan, H., 2017b. A novel peat biochar
supported catalyst for the transesterification reaction. Energy Convers. Manag.
139, 89–96. https://doi.org/10.1016/j.enconman.2017.02.039.
Wiersema, J. H., GRIN Taxonomy. US National Plant Germplasm System. Checklist
dataset (2019) https://doi.org/10.15468/ao14pp accessed via GBIF.org on 2019-
08-21.
Wilson, K., Hardacre, C., Lee, A.F., Montero, J.M., Shellard, L., 2008. The application of
calcined natural dolomitic rock as a solid base catalyst in triglyceride
transesterification for biodiesel synthesis. Green Chem. 10, 654–659. https://
doi.org/10.1039/B800455B.
Xie, W., Huang, X., 2006. Synthesis of biodiesel from soybean oil using
heterogeneous KF/ZnO catalyst. Catal. Lett. 107, 53–59. https://doi.org/
10.1007/s10562-005-9731-0.
Xie, W., Li, H., 2006. Alumina-supported potassium iodide as a heterogeneous
catalyst for biodiesel production from soybean oil. J. Mol. Catal. A. 255, 1–9.
https://doi.org/10.1016/j.molcata.2006.03.061.
Xiong, Y., Miao, W.F., Wang, N.N., Chen, H.M., Wang, X.R., Wang, J.Y., Tan, Q.I., Chen,
S.P., 2019. Solid alcohol based on waste cooking oil: Synthesis, properties,
micromorphology and simultaneous synthesis of biodiesel. Waste Manag. 85,
295–303. https://doi.org/10.1016/j.wasman.2018.12.036.
Zhao, C., Yang, L., Xing, S., Luo, W., Wang, Z., Lv, P., 2018. Biodiesel production by a
highly effective renewable catalyst from pyrolytic rice husk. J. Clean. Prod. 199,
772–780. https://doi.org/10.1016/j.jclepro.2018.07.242.