Journal of Cleaner Production 394 (2023) 136362

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Journal of Cleaner Production

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

Sulphonic-acid functionalized novel Limonia acidissima carbonaceous

catalyst for biodiesel synthesis from Millettia pinnata oil: Optimization,
kinetics, thermodynamics and cost analysis
Nabanita Ghosh a, Rhithuparna D.a, Rexona Khatoon a, Samuel Lalthazuala Rokhum b,
Gopinath Halder a, *
a
Department of Chemical Engineering, National Institute of Technology Durgapur, Durgapur, 713209, West Bengal, India
b
Department of Chemistry, National Institute of Technology Silchar, Silchar, 788010, Assam, India

A R T I C L E I N F O A B S T R A C T

Handling Editor: Maria Teresa Moreira In order to overcome the current fuel crisis affecting transportation, expanding environmental pollution chal­
lenges, and depletion of natural oil resources, a sustainable alternative to petroleum fuels must be developed.
Keywords: Biodiesel has been accepted as a promising substitute for petro-fuels in many countries because it can fulfill the
Biodiesel requirements of the transportation industry. The present research introduces biodiesel production from Millettia
Catalyst reusability
pinnata (Karanja) oil utilizing waste wood apple (Limonia acidissima) shell in deriving carbonaceous catalysts in
Limonia acidissima
view of waste valorization for green energy generation towards alleviation of its ever-growing demand. The
Millettia pinnata
Central composite design feedstock had a high free fatty acid (FFA) concentration based on proximate analysis, which indicated that an
Cost analysis acid catalyst was required for fuel production. Analysis of the prepared catalyst was done by SEM, EDAX, FTIR,
XRD, and BET. The optimization of esterification was performed with the RSM central composite design (CCD)
experimental matrix, while the reaction time was 1.5 h at 55◦ C with 4 wt. % catalyst under 650 rpm and 50% w/
w alcohol concentration. The actual yield was reported to be 98.95% under ideal conditions. The fuel charac­
terization revealed that KOME (Karanja oil methyl ester) possesses physico-chemical characteristics suitable for
biodiesel as per ASTM standards. Kinetic studies showed that the esterification follows pseudo-first-order kinetics
with an activation energy of 62.61 kJ mol − 1. The thermodynamic study confirmed that the acid-catalyzed
esterification reaction is endothermic and non-spontaneous. The production cost of catalyst per kg of biodiesel
was estimated to be $0.1649.

conventional fossil fuels (Nawaz et al., 2021). Biodiesel is prepared

1. Introduction
Global energy consumption is increasing daily, with an estimated
56% increase from 2010 to 2040, according to the Energy Information
Administration (US EIA, 2013). A significant cause of this issue is the rise
in population resulting in an improved lifestyle along with urbanization.
As a result, efforts are being made to actively address environmental
issues, including the depletion of fossil fuels (natural gas, petroleum, and
coal) and their rising costs through research and development of other
alternative energy sources, such as renewable energy. In this scenario,
biodiesel, made up of long-chain fatty acid methyl esters (FAME), has
drawn attention on a global scale as an easily deployed substitute to
commercially by esterification/transesterification reaction in which
various oil feedstocks react with an alcohol in the presence of different
catalysts such as homogeneous, heterogeneous, enzymatic, or nano­
catalysts to form FAME and glycerol as a by-product as shown in Fig. 1.
Lower CO2 emission, non-toxicity, high flash point, zero sulfur content,
biodegradable nature, and substantial hexadecane (cetane) content are
reasons biodiesel is considered an alternative to fossil fuels (Shan et al.,
2018; Mota et al., 2019). Additionally, it can be blended straight into the
present diesel engine without any modification.
Feedstocks, including edible and non-edible ones, spent grease,
miscellaneous sources, and animal fats, are used in biodiesel production
(Karmakar and Halder, 2019). Edible oil crops still comprise around

* Corresponding author. Chemical Engineering Department, National Institute of Technology Durgapur, Mahatma Gandhi Avenue, Durgapur, 713209, West
Bengal, India.
E-mail addresses: ng.21ch1102@phd.nitdgp.ac.in (N. Ghosh), rd.22ch1105@phd.nitdgp.ac.in (D. Rhithuparna), rk.21p10132@mtech.nitdgp.ac.in (R. Khatoon),
rokhum@che.nits.ac.in (S.L. Rokhum), gopinath.halder@che.nitdgp.ac.in (G. Halder).

https://doi.org/10.1016/j.jclepro.2023.136362
Received 1 November 2022; Received in revised form 31 January 2023; Accepted 5 February 2023
Available online 9 February 2023
0959-6526/© 2023 Elsevier Ltd. All rights reserved.
N. Ghosh et al. Journal of Cleaner Production 394 (2023) 136362

Abbreviations AGC Agitation costs

SEM Scanning electron microscope
FFA Free fatty acid BET Brunauer-Emmett-Teller
AV Acid value FTIR Fourier transform infrared spectrometer
FAME Fatty acid methyl esters XRD X-ray diffraction
NIT National Institute of Technology EDAX Energy-dispersive X-ray spectroscopy
OFAT One factor at a time GC-MS Gas chromatography-mass spectrometry
BBD Box-Behnken design KV Kinematic viscosity
CCD Central composite design AP Adequate precision
PBD Plackett-Burman design MeOH Methanol
OA Orthogonal array KO Karanja oil
RSM Response surface methodologies SNR Signal-to-noise ratio
KOME Karanja oil methyl ester SMC Cost of starting material
NMR Nuclear magnetic resonance SRC Cost of size reduction
GC Gas chromatography HC Heating cost
TGA Thermogravimetric analysis WC Washing cost
N2 Nitrogen IC Impregnation cost
ADC Acid-doped catalyst CC Carbonization cost
DRC Drying cost ANC Activation costs
IEC Inert environment creation costs RMC Raw material creation cost
SC Steam preparation cost CCH Cost of chemicals

95% of the global feedstock utilized for biodiesel synthesis because they
are simple to convert (Demirbas, 2009). The price growth of consumable
oils is mainly due to their extensive use in the manufacturing of fuels
(Raj and Sahayaraj, 2010). Hence, researchers have recently employed
non-edible oils for biodiesel production, including Karanja, jatropha,
and castor oil. The Karanja tree (Pongamia pinnata) is a medium-sized
evergreen tree belonging to the Leguminosae family, with an average
height of 12–15 m (Atabani et al., 2013; Bobade and Khyade, 2012). The
large canopy and fragrant flowers make it an ideal plant for landscaping
along highways. These trees can thrive in various soil types, including
sandy, rocky, and clayey, and are resistant to high saline conditions.
Moreover, both their roots and canals prevent soil erosion. It takes
Karanja 4–7 years to mature its fruits after it gets planted. The seeds are
flat and elliptical, with a length of 3–6 cm and a width of 2–3 cm. The
reddish-brown seeds of Karanja fruits contain 1 or 2 kernels that
resemble human kidneys. Approximately 30–40% of the oil content is
present in the Karanja seed kernel, and nearly 900–9000 kg of oil gets
produced per hectare. The bitter taste, dark brown color, and unpleasant
smell are the significant constraints of this oil for human consumption
(Bobade and Khyade, 2012). With an annual production of 13,500
million tons, it is one of the most potentially valuable oils, but only 6% of
its oil is used (Khayoon et al., 2012). Compared with jatropha oil, Kar­
anja oil is more economical and emits fewer harmful substances (Karmee
et al., 2004). It is most common for biodiesel to be produced with
methanol, although higher alcohols are preferred since they combine
better with oils during transesterification of triglycerides. However, the
less polar alkyl groups in higher alcohols prevent them from reacting
with the FFAs; hence methanol is often considered for FFA esterification.
Having high FFA content, Karanja oil is appropriate for biodiesel
production using an acid catalyst by esterification. A large quantity of
FFA in the feedstock can degrade the alkaline catalyst’s efficacy as they
react with the catalyst, generating soap and water production during the
saponification process. Thiruvengadaravi et al. used sulfonated zirconia
as a solid acid catalyst to esterify the high FFA Karanja oil. A reduction in
acid value from 12.27 mg KOH/g to 1.3 mg KOH/g, confirming the
conversion, was observed during this process (Thiruvengadaravi et al.,
2012). Similarly, Karmakar et al. converted FFA in Karanja oil using
sulfonated Delonix regia pods. A 99.86% FFA conversion was observed in
the study (Karmakar et al., 2020a). Due to its many benefits, such as
reusability, ease of separation, reduced corrosion, safety, time savings,
and cost, heterogeneous catalysts make it more economical and practical
to catalyze biodiesel production (Karmakar et al., 2020b). Zeolites,
metal oxides, and silica are readily available and used directly as het­
erogeneous catalysts (Narowska et al., 2019). In addition, certain
biomass-derived activated carbon such as paper sludge, flamboyant
pods (Dhawane et al., 2016a), fish scales (Chakraborty and Das, 2012),
and Mesua ferrea linn (MFL) (Bora et al., 2018) seed shells are func­
tionalized and are employed as heterogeneous catalysts. Wood apple
fruit (Limonia acidissima) is a native crop of India, and its shells are
inexpensive and widely available (Chandrakala and Upadhyay, 2019).
The outcome of an experiment can be determined using batch studies
by finding the correct range of parameter values. The reaction param­
eters must be optimized to achieve the highest possible product yield. It
takes great time and energy to manually optimize one factor at a time
(OFAT). As a result, soft-computational methods are now employed for
process optimization. These methods include Plackett-Burman design
(PBD) or Taguchi OA (orthogonal array), which are factorial method­
ologies illustrating a process’s individual effects on a given response
(Karmakar et al., 2021a, 2021b). At the same time, Box-Behnken design
(BBD) and central composite design (CCD) are response surface meth­
odologies (RSM) that use surface plots to illustrate interacting process
parameters (Karmakar et al., 2022). CCD and BBD cover a broader range

Fig. 1. Esterification reaction for the production of biodiesel.

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N. Ghosh et al. Journal of Cleaner Production 394 (2023) 136362

of reaction conditions than PBD and Taguchi OA, which do not run all respectively.
recommended combinations. The BBD approach is highly efficient, but it
has a few drawbacks. It is not rotatable, and its runs do not include
2.2. Synthesis of sulfonic acid functionalized carbon catalyst
corner points. It is possible to overcome the disadvantages of the BBD
model using CCD, which has the advantage of being rotatable and
Initially, tap water was employed to wash the wood apple shells to
including corner points in its runs (Joshi et al., 2018). CCD optimizes the
remove impurities and dust particles, followed by cleaning with deion­
experiment using values outside the designated model space, leading to
ized water to eliminate residual ions. Before grinding and size reduction,
a more accurate model. ANOVA studies help test mathematical models’
the apple shells were sundried for 2–3 days, followed by drying in an air
validity and accuracy by using the data obtained through statistical
oven at 80 ◦ C to remove excess moisture. The dried shells were subjected
model evaluation (Mukherjee et al., 2020; Ghadge and Raheman, 2006).
to thermogravimetric (TGA) (Shimadzu, model C30574700290, Japan)
Several acid-functionalized heterogeneous catalysts are already re­
analysis to confirm the thermal stability and carbonization temperature
ported for biodiesel production, e.g., Aminophosphonic acid resin D418,
ranging from 30 ◦ C to 700 ◦ C at the rate of 10 ◦ C/min with a continuous
Oil cake waste-SO3H, Sulfated Zirconia, C–SO3H, CMR-DS-SO3H, Co­
nitrogen (N2) flow of 19.8 mL/min (Dhawane et al., 2015). Following,
conut shell-SO3H, etc. Karmakar et al. performed an acid-catalyzed
the shells were carbonized in the muffle furnace at 300 ◦ C, as depicted in
esterification reaction using sulfonated Delonix regia char to produce
Fig. 2, for 1.5 h under continuous N2 flow. This ensures no water, and the
biodiesel from mahua oil with a yield of 97.04% (Karmakar et al.,
volatile compound is present in the carbonized char. Consequently, the
2020b). Cao et al. employed sulfonated Sargassum horneri carbon cata­
shells were steam activated to enhance surface properties for 1.5 h at
lysts to convert oleic acid into biodiesel. The conversion observed was
350 ◦ C under the pressure of 1.5–2 kg/cm2 or 21.34–28.45 psi. Wet
96.4% (Cao et al., 2021). A heterogeneous carbonaceous acid catalyst
impregnation was utilized to dope H2SO4 with carbonized char. For the
was developed by Medina-Valtierra et al. that converted waste frying oil
synthesis of the waste-derived acid catalyst, the ratio of carbonized char:
into biodiesel at a conversion rate of 83.7% (Medina-Valtierra et al.,
H2SO4 was maintained at 1:5 w/v for 12 h while being stirred
2017). Similarly, by doping carbonized bamboo char with H3PO4, Tang
magnetically at 600 rpm at 120 ◦ C (Dhawane et al., 2016b). The solu­
et al. synthesized a carbon-based solid acid catalyst. The conversion rate
tions were frequently rinsed with water, filtered, and dehydrated for
for the esterification of oleic acid using this catalyst and methanol was
characterization to eliminate the excess chemicals. The complete elim­
97.3% (Tang and Niu, 2019). However, synthesis of these catalysts in­
ination of the acid was ensured by confirming the pH of the filtered
volves multi-steps and harsh reaction conditions that increase the
water after continuous washes. The final catalyst was called an “acid
overall cost and reduce the environmental compatibility of biodiesel
doped catalyst” (ADC) that assists in the esterification of Karanja oil. The
production, thereby limiting their industrial application. Nevertheless,
schematic diagram of the catalyst synthesis process is shown in Fig. 3.
synthesizing catalysts prepared from waste biomass could provide an
alternative, sustainable, and cost-effective biodiesel production. On the
other hand, numerous other investigations into wood apple shells have 2.3. Characterization of the catalyst
also been published. Malarvizhi et al. investigated the sorption isotherm
and the kinetics of methylene blue uptake using activated carbon from Activated and acid-doped catalysts were tested for surface charac­
wood apple shells (Malarvizhi and Sulochana, 2008). Similarly, teristics with the help of Scanning electron microscope (SEM) (JEOL
Mahendra et al. used an activated carbon electrode made from wood JSM- 6030, India). The samples were tested through Brunauer-Emmett-
apple shells for removing Cr (VI) and fluoride from feed solutions Teller (BET) to identify surface area and pore volume using Smart Sorb
(Gaikwad and Balomajumder, 2018). In this paper, an acid-doped 92–93 (Smart Instruments, India) at − 196 ◦ C through the N2 adsorption-
catalyst has been synthesized from a waste wood apple shell. A desorption process. (FTIR), Fourier transform infrared spectrometer was
detailed analysis of numerous reported literatures in the past few years used to check the raw, acidic char (FTIR C109292, spectrometer USA). A
reveals that till now, no researcher has used wood apple shell-based acid pellet of KBr is scanned as the backdrop in the process, and then pellets
catalyst for the production of biodiesel, mainly from inedible Karanja containing a tiny amount of material combined with KBr are used to
oil. In the current study, we report a novel sulfonated carbon catalyst analyze the functional groups. The determination of the amorphous
derived from waste Limonia acidissima shells for producing biodiesel structure of the char was performed through X-ray diffraction (XRD)
from high FFA Karanja oil and methanol through esterification. A kinetic analysis by (D8 ADVANCE BRUKER AXS, Germany) for structural
and thermodynamic study was conducted to determine the reaction’s changes in the char after doping through scanning by Cu-Kα parallel
rate constant, activation energy, and thermodynamic parameters. A cost
study of catalyst production reveals that its preparation is a relatively
inexpensive strategy with excellent outcomes.

2. Materials and method

2.1. Materials used

The abundantly available Limonia acidissima (wood apple) shells

were collected and utilized as starting materials for synthesizing inert
support for catalyst preparation. During the monsoon, wood apple shells
were gathered from the surrounding National Institute of Technology
(NIT) Durgapur premises. Karanja oil as feedstock for biodiesel pro­
duction was obtained from local vendor at free of cost for performing the
current study. The oil was purified and put through the first round of
investigative testing to determine its physicochemical characteristics.
This work used chemicals of laboratory grade, including methanol
(99.5%; Merck, India) for esterification, 2-propanol as a solvent,
phenolphthalein (as an indicative) for titration, and to quantify FFA %
and acid value. H2SO4 (conc.) and deionized water were obtained from Fig. 2. Thermo-gravimetric analysis (TGA) and derivative thermo-gravimetry
Merck, Mumbai, India, and Sartorius A.G., Gottingen, Germany, (DTG) of raw wood apple shell.

3
N. Ghosh et al. Journal of Cleaner Production 394 (2023) 136362

Fig. 3. Schematic representation of catalyst preparation.

beam radiation over 2θ of 5◦ –45◦ at a step size of 0.02◦ (Karmakar et al.,

56.1 × M × t
2020a). Moreover, the effective integration of acid was also checked by Acid Value = (2)
m
energy-dispersive X-ray spectroscopy (EDAX) utilizing OXFORD
INCAX-sight for computing the fraction of the quantity of sulfur-doped
after acid impregnation. 2.5. Design of experiments using CCD matrix

The FFA conversion % of esterified Karanja oil to methyl ester is

2.4. Preliminary Karanja oil analysis influenced by various reaction parameters, viz. methanol to oil ratio,
catalyst loading, reaction temperature, reaction time, etc. As a result, it
The efficiency of the conversion process solely depends on the acid is essential that these reaction parameters be optimized for use in an
value (AV) and FFA % of the feedstock oil. The characteristics of the experimental table that uses different process parameters and that is
Karanja oil were identified in accordance with the ASTM standard then applied to create a formula that can determine the maximum
procedure. The oil was freed of residual water and impurities by heating condition through the distinct and collaborative influence of various
above 60 ◦ C, and filtration was done by vacuum to obtain pure Karanja varying parameters. For instance, the values extend the maximum and
oil. The oil was analyzed for its physical and chemical characteristics: minimum value for optimization, the generated quadratic second-order
acid value, relative density, flash point, water content, calorific value, equation performs repetitive runs with barely varying reaction param­
cetane no, fire point, and kinematic viscosity. Table 1 shows the fatty eters clustered around the center point of each reaction condition. Each
acid content of Karanja oil as determined by gas chromatography-mass reaction parameter has values ranging from lowest (− ), passing through
spectrometry (GC-MS). The FFA% and acid values were performed with focus point (0), to greatest (+). Five levels (marked as -α, − 1, 0, +1, +α)
titration assembly (ASTM procedure D974). A certain quantity of oil was are tested for each parameter in the current task, as explained in Table 2.
dissolved in 20 mL of 2-propanol, in which 1–2 drops of phenolphthalein The number of total desired experimental steps is designated as N, which
was used as an indicator (Karmakar et al., 2020b). 0.01 M KOH mixture is the summation of three categories of experimental steps, i.e., the total
was used to titrate the solution until a steady pink color (lasting for 30 s) number of factorial runs F = 2n (16 runs), the total number of axial runs
developed. Finally, by applying Equations (1) and (2), where M denotes E = 2(n) (8 runs) and the total number of center run C = nc (6 runs), as is
the strength of the employed KOH mixture, w denotes the weight of oil, described in the following Eq. (3):
and t denotes the titre value. It is possible to directly compute the AV
N = 2n + 2(n) + nc (3)
(mg KOH/g oil) and FFA % (wt. % of oleic acid) of the feedstock oil.
KOH’s molecular weight is 56.1, oleic acid’s molar weight is 282, and The accuracy of the results acquired from each experiment was
the FFA standard for oleic acid is 0.1 M (Karmakar et al., 2018). checked with the quadratic regression equation indicating the maximum
biodiesel yield. The model and sum of squares for individual parameters
282 × M × t
Free Fatty Acid % = (1) were utilized to find the contribution factor for each parameter to
m
investigate the influence of final biodiesel yield utilizing Eq. (4).
( )
ssf
Contribution factor (%) = × 100 (4)
ssT
Table 1
Fatty acid percentage of Karanja oil.
Fatty acid Chemical name Structure Weight % Table 2
Palmitic Hexadecanoic 16:0 10–11 Process parameters and their values at different levels.
Linoleic Cis-9, cis-12-octadecenoic 18:2 18–19
Name Units Low High -alpha +alpha
Stearic Octadecanoic 18:0 6–7
Oleic Cis-9-octadecenoic 18:1 48–49 A Catalyst concentration % w/w 3 5 2 6
Behenic Docosanoic 22:0 4.5–5.5 B Methanol concentration % w/w 40 60 30 70
Arachidic Eicosanoic 20:0 4–5 C Time min 60 120 30 150
Lignoceric Tetracosanoic 24:0 2.5–3.5 D Temperature ◦
C 50 60 45 65

4
N. Ghosh et al.
where, SSf = sum of squares of a particular factor, SSt = sum of squares
of the model.
2.6. Experimental procedure
A round bottom flask with three mouths was utilized to esterify the
Karanja oil. A thermometer that quantifies the temperature of the re­
action mixture was attached to one of the flask’s three necks, a
condenser was attached to the middle neck to help retain the methanol
in the system, and the remaining neck was used for the addition of the
catalyst inside the reaction mixture. The reflux condenser aids in
maintaining the methanol percentage considerably above the necessary
level stoichiometrically because methanol does not react in the reaction
mixture. The catalyst was added using the middle neck. After heating the
required feedstock oil and methanol, the desired catalyst was added to
the desired temperature. The stirring speed of 650 rpm was considered
optimum while working with Karanja oil and methanol using acid-based
esterification. Therefore, it was set constant for this optimization study.
Apart from stirring speed, other reaction parameters were varied to get
an optimized design matrix, including each set’s optimum parametric
ratios performed to get experimental results. After the reaction, the
mixture was cooled to ambient temperature to halt additional conver­
sion. After that, the catalyst was separated using filtration, and methanol
was then retrieved utilizing distillation by a rotary evaporator. In order
to get rid of contaminants and eluted acidic functional groups, the
esterified oil must be rinsed with water. The esterified oil was then
poured into a separatory funnel after being washed until the water’s pH
was neutral. The oil sample was ultra-centrifuged before this step to
eliminate more contaminants. The FAME yield of the esterified oil was
measured by titration analysis that identifies the FFA percentage as a
Fig. 4. (a) EDAX spectral analysis of steam-activated catalyst. (b) EDAX spectral analysis of H2SO4 impregnated catalyst.
5
Journal of Cleaner Production 394 (2023) 136362
direct measure of the conversion of FFA into FAME.
3. Results and discussion
3.1. Catalyst characterization
The obtained catalyst was studied to define its physical qualities after
being wet impregnated with H2SO4 on the fabricated char made from
wood apple shells. After impregnating the H2SO4 on the carbonized
char, a substantial decline in surface area and pore volume was noticed,
which was mostly due to the H2SO4’s good dispersion and adsorption on
the catalyst support. BET studies of activated char and ADC indicated
surface area and pore volume. The results highlighted that: (a) activa­
tion of the biochar with steam increases surface area by creating mi­
cropores on the surface of the char, and (b) H2SO4 impregnation
drastically closes the pores of ADC. The pore volume and surface area for
activated char are 0.0704 cm3/g and 321.52 m2/g, respectively, ac­
cording to BET data, whereas these values are 0.3126 cm3/g and 807.4
m2/g for ADC. The presence of doped sulfur in the prepared catalyst can
be confirmed by EDAX analysis. The elemental structure for the acti­
vated catalyst is shown in Fig. 4a, where sulfur is present in insignificant
amounts in the activated char catalyst accounting for only 1%. Never­
theless, the doped resulted catalyst is perceived to be C = 21%, O = 24%,
S = 51%, Na = 1%, K = 1% and Ca = 1% as shown in Fig. 4b (Karmakar
et al., 2020a; Show et al., 2022). It is evident in the SEM micrographs
that have been provided for both sulfonated carbon and steam-activated
carbon. According to Fig. 5a, the catalyst support features a surface
structure that can adsorb functional groups as a result of the passage of
steam. This indicates that the activation process followed by super­
heated steam could completely modify the char’s surface characteristics
by generating pores. As further evidenced by Fig. 5b, catalytic functional
N. Ghosh et al.
Fig. 5. SEM image of (a) steam-activated wood apple (b) H2SO4 impregnated wood apple.
groups have significantly adhered to the surface and pores of the sul­
fonated carbon support, resulting in surface smoothening and pore
plugging. Fig. 6 depicts the FTIR data for steam-activated and sulfonated
carbon catalysts after acid impregnation. The appearance of peaks at
various characteristic wavenumbers are as follows for activated carbon:
940 cm− 1 explains the presence of single bond C–H alkene stretches,
1526 cm− 1 shows the presence of C–C stretch, 1680 cm− 1, and 1692
cm− 1 represents C– – C alkene stretches of weak and medium bond
strength respectively, For the sulfonated carbon, following peaks were
observed: 1102 cm− 1 is characteristic of the sulfoxide group, while the
very sharp peak at 1158 cm− 1 confirms the presence of the H2SO4
adsorption on the carbon support. Fig. 7 depicts the XRD analysis, which
helps understand the samples’ amorphous structure. From the graph, as
shown in Fig. 7a, it is seen that characteristic peaks observed for ADC
indicate proper sulfonation. The diffraction peaks are identified using a
standard JCPDS library (Thiruvengadaravi et al., 2012). Fig. 7 shows the
presence of different peaks specific for each sample: activated carbon
and doped carbon can be seen at 24.994◦ and 40.89◦ , which confirms
that the support is carbonaceous in nature. The curve for the ADC
catalyst shows broad peaks in the range between 15◦ and 25◦ and be­
tween 35◦ and 45◦ , which are indicative of proper H2SO4 that have
shown similarity with some of the peaks obtained from the standard
dimethyl sulfate. These have been marked in Fig. 7 (24.484◦ , 25.56◦ ,
40.88◦ ) along with the planes (131, 003 and 511, respectively).
Fig. 6. FT-IR plot of steam-activated carbon from wood apple and sulfonated
carbon from wood apple.
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Journal of Cleaner Production 394 (2023) 136362
3.2. Fuel characterization
To determine the formation and chemical structure of the synthe­
sized KOME, 1H NMR and 13C NMR (Nuclear magnetic resonance) were
performed on (AVNACE NEO500, Switzerland) series instrument with a
spectrometer frequency of 500 MHz. GC-MS was used to investigate the
chemical composition of the synthesized KOME. GC-MS was performed
on Agilent Model 8890 instrument equipped with Single Quadrupole
Mass Spectrometer (5877 B MSD) analyzer. (FTIR), Fourier transform
infrared spectrometer was utilized to confirm the presence of ester
content (FTIR C109292, spectrometer USA).
After the completion of the esterification reaction, the produced
KOME was checked by performing 1H NMR and 13C NMR analysis and
was compared with raw Karanja oil, as shown in Fig. 8. Fig. 8a repre­
sents the 1H NMR spectrum of FAME. The appearance of a peak at 3.66
ppm confirms the formation of FAME (Fig. 8a). The singlet peak at 3.66
ppm represents the methoxy protons of FAME, and the triplet peak at
2.31 ppm can be attributed to α− CH2 protons. Raw Karanja oil and
synthesized KOME have different NMR spectra, as evidenced by the lack
of methoxy protons at 3.6 ppm in raw oil (Fig. 8c), indicating that
Karanja oil has been converted to KOME. From 13C NMR, the appearance
of peaks at 51.5 ppm for the –OCH3 group (Fig. 8b), carboxyl peaks
around at 174.49 and 176.87 ppm, olefinic carbons at 127–130 ppm
(Fig. 8b) confirms the formation of FAME (Chatterjee et al., 2021). The
FAME conversion was found and is reported to be 98.11% at optimized
reaction parameters, as discussed in the sections below.
2AMe
C = 100x (5)
3ACH2
Here, C is the conversion percentage of Karanja oil, AMe is the integration
area of the methoxy protons and ACH2 is the integrated area of the
α− CH2 protons.
The chemical composition of the synthesized KOME (Karanja oil
methyl ester) was obtained by GC-MS analysis (Fig. 9). Furthermore, the
quantitative measurement of KOME components was calculated by
using the peak areas of KOME and internal standard peak area (methyl
heptadecanoate, C17:0). The obtained data was presented in Table 3.
Fig. 10 shows the FTIR spectrum of synthesized biodiesel using an
acid-doped catalyst. In polar molecular environments, methylene bands
are evident in 2921–2855 cm− 1. This is evident by the peaks 2920.23
and 2850.79 cm− 1. The presence of the carbonyl band in oil is observed
in the peak 1743.64 cm− 1 (Chatterjee et al., 2022). This sharp and long
peak is because of the ester group in oil. Aliphatic C–H bands are
observed at 1465.90, 1369.46, and 725.24 cm− 1, and C–O stretch bands
were observed at 1161.15 cm− 1. Peaks in the range 1070–1150 cm− 1 are
due to ethers -C-O stretch. This is evident due to the presence of 1091.71
N. Ghosh et al.
Fig. 7. XRD plot of (a) steam-activated wood apple shell and (b) sulfonated wood apple shell after H2SO4 doping.
Fig. 8. 1H NMR and 13
C NMR, of KOME (a,b) and raw Karanja oil (c,d).
cm− 1.
As shown in Table 11, the fuel qualities are found to be within
acceptable commercial standards for biodiesel by ASTM characteriza­
tion testing. After esterification, the product has a very low kinematic
viscosity (KV), which indicates favorable flow characteristics and ease of
atomization during the injection. Adequately high cetane number of a
fuel indicates good quality, while its higher aniline point indicates that it
is paraffin-rich and has clean-burning properties. The fuel’s high flash
and fire points signify the sample’s high thermal stability. The fuel’s
high calorific value indicates that it also has a high energy content.
Because the fuel has a low AV and FFA, which indicate that it is hardly
corrosive, it can be used in engines without harming the mechanical
components.
7
Journal of Cleaner Production 394 (2023) 136362
3.3. Modelling and analysis of data using response surface methodology
(RSM)
Optimization of the esterification reaction was carried out with the
experimental matrix of the RSM central composite design (CCD). Ac­
cording to experimental runs, biodiesel conversion ranged from 80.96 to
98.95%. Table 4 displays the actual and predicted result for each
experimental run. Meanwhile, the coded factors A-D influence the bio­
diesel yield, as described in Eq. 6
Biodiesel yield (Y) = 98.75–0.2863A + 0.9204B + 2.99C + 1.47D - 0.9544
AB - 0.0294 AC − 2.79AD - 0.7919BC + 0.5669BD − 1.23CD - 3.08A2
-1.42B2 -1.88C2 -1.40D2 (6)
N. Ghosh et al. Journal of Cleaner Production 394 (2023) 136362

Fig. 9. Gas chromatography analysis of the KOME obtained.

design space precisely. The model’s adequate precision (AP) value is

Table 3
112.67, much greater than the minimum required value of 4. High AP
Gas chromatography analysis results.
values indicate that the experimental results were error-free, i.e., ac­
Sl. Retention Name Structure Area curate. Thus, the AP value indicates the signal-to-noise ratio (SNR)
No time %
(Show et al., 2022).
1. 25.853 Hexadecanoic acid, 10.59 The regression model’s quality is evaluated using diagnostic plots
methyl ester
(Fig. 11). Fig. 11a compares the predicted and actual conversion of
2. 30.004 9,12- 10.19
Karanja oil to KOME. The proximity of data points to the fit regression
Octadecadienoic
acid (Z, Z)-, methyl line implies a good estimation of the response for changes in the inde­
ester pendent variables A-D. The ANOVA model is evaluated on how well it
3. 30.148 cis-13- 49.78 fits assumptions by the residuals, i.e., the differences between actual and
Octadecenoic acid, predicted values. Assessing the residuals for a normal distribution is
methyl ester
crucial in determining whether the regression model is acceptable.
4. 30.729 Methyl stearate 5.14 Fig. 11b is the plot between studentized residuals and predicted con­
version. The plot’s random distribution of residuals indicates no corre­
5. 38.093 Methyl 20-methyl- 1.21
lation between original observation and response values. It is, therefore,
heneicosanoate
not necessary to transform the response parameter. Fig. 11c illustrates
the relationship between studentized residuals versus normal distribu­
Where A, B, C, and D refer to catalyst loading, methanol concentration, tion. As shown in the Figure, most of the data follow a straight line
reaction time and temperature, respectively. The "+" sign indicates a rather than the unusual S-shape indicative of a normal distribution for
positive influence of that term on the reaction process caused by a studentized residuals (Jaliliannosrati et al., 2013). A comparison of the
specific level of the process parameter in the regression equation, residuals with the experimental run is shown in Fig. 11d. Since the ex­
whereas the "-" sign indicates that a term in the equation negatively periments are subjected to noise, large residual differences between the
impacts the process according to the parameter level chosen. The sig­ runs are observed. No errors are recorded with the fitted model, as all
nificant parameters can be summed up according to their contributing residuals fall in the range of 4.00 (Mostafa Marzouk et al., 2021).
factors: catalyst loading = 0.24%, methanol concentration = 2.48%,
reaction time = 26.29%, and temperature = 6.29%, as shown in Table 5.
3.5. Parametric analysis of conversion

3.4. Statistical analysis through ANOVA
As shown in Table 6, the outcomes of the experimental runs are
analyzed and summarized using statistical analyses of variance
(ANOVA). F-value (Fischer’s exact test) for the regression model
developed was high enough to indicate the significance of the model. A
p-value <0.0001 implies that there is only a 0.01% possibility that the
values in the proposed model were acquired by chance, along with the
high F-value, providing further assurance that the results were error-free
(Mukherjee et al., 2020). Additionally, the R2 values for predicted and
adjusted data (0.9949 and 0.9981, respectively) differed by less than
0.2, as seen in the model comparison and fit statistics, demonstrating a
strong connection between experimental and theoretical data. This led
to the inference that the selected model could be utilized to explore the
Experimental conversion of Karanja oil to KOME was evaluated using
3D response surface plots (Fig. 12) to determine the influence of inde­
pendent parameters A-D (A = catalyst loading, B = methanol (MeOH)
concentration, C = reaction time, and D = reaction temperature)
(Sharma et al., 2019). Fig. 12a illustrates how the concentrations of the
catalyst and MeOH affect conversion. The conversion increased with
increasing catalyst and MeOH concentration to reach its maximum at 4
wt% and 50% (w/w), respectively. Since esterification is reversible,
extending the reaction conditions beyond the optimum value can
moderately reduce conversion. When added more than necessary,
MeOH dilutes the system, impairing conversion rates and reactant in­
teractions. Low quantities of MeOH, in contrast, are inadequate to stop a
backward reaction (Ramachandran et al., 2011). Similarly, this study
maintained the catalyst concentration between 2 and 6% w/w, with 4%

8
N. Ghosh et al. Journal of Cleaner Production 394 (2023) 136362

Fig. 10. FTIR spectrum of the KOME obtained.

Table 4
CCD experimental design matrix for esterification of Karanja oil to KOME.
Run Space Catalyst conc. (% w/w) Methanol: conc. (% w/w) Time (Min) Temperature (◦ C) Predicted FFA Conversion Actual FFA Conversion
No: Type (A) (B) (C) (D) % %

1 Center 4 50 90 55 98.75 98.58

2 Factorial 3 60 120 60 98.95 98.92
3 Factorial 5 40 60 60 86.30 86.39
4 Axial 2 50 90 55 87.00 86.89
5 Center 4 50 90 55 98.75 98.95
6 Factorial 3 40 60 60 90.48 90.52
7 Factorial 3 60 60 60 96.95 97.09
8 Factorial 3 40 120 60 95.65 95.48
9 Axial 4 50 150 55 97.24 97.41
10 Center 4 50 90 55 98.75 98.72
11 Factorial 5 40 120 60 91.36 91.36
12 Axial 6 50 90 55 85.85 85.99
13 Factorial 5 60 120 60 90.84 90.74
14 Axial 4 30 90 55 91.22 91.14
15 Center 4 50 90 55 98.75 98.81
16 Factorial 5 40 120 50 97.59 97.66
17 Axial 4 70 90 55 94.90 95.02
18 Factorial 5 60 60 50 88.00 88.38
19 Factorial 5 60 120 50 94.81 94.52
20 Factorial 3 40 60 50 80.65 80.96
21 Factorial 3 60 120 50 91.77 91.9
22 Center 4 50 90 55 98.75 98.79
23 Factorial 5 60 60 60 88.95 88.7
24 Factorial 3 40 120 50 90.74 90.75
25 Axial 4 50 90 45 90.21 90.12
26 Axial 4 50 90 65 96.07 96.19
27 Axial 4 50 30 55 85.26 85.12
28 Center 4 50 90 55 98.75 98.66
29 Factorial 3 60 60 50 84.85 84.6
30 Factorial 5 40 60 50 87.62 87.4

showing maximum conversion. Due to the heterogeneous nature of the

Table 5 catalysts, an excess amount can cause diffusional resistance between the
Parametric optimum values and contribution percentage for FFA conversion %.
oil and alcohol (Banani et al., 2015).
Parameter Contribution factor Optimum value An illustration of the impact of reaction time and catalyst dosage on
Catalyst concentration (% w/w) 0.24% 4 FFA conversion is shown in Fig. 12b. The conversion increased signifi­
Methanol: concentration (% w/w) 2.48% 50 cantly with an increase in catalyst amount due to the availability of more
Time (Min.) 26.29% 90 active sites. Although the catalyst concentration was increased further,
Temperature (◦ C) 6.29% 55
the maximum FFA conversion was detected. The optimum conversion

9
N. Ghosh et al. Journal of Cleaner Production 394 (2023) 136362

Table 6
Statistical ANOVA result for esterification of Karanja oil.
Source Sum of Squares df Mean Square F-value p-value Accuracy test

Parameters Value

Model 817.63 14 58.40 1107.13 <0.0001 significant R2 0.9990

A 1.97 1 1.97 37.28 <0.0001 – Adjusted R2 0.9981
B 20.33 1 20.33 385.44 <0.0001 – Predicted R2 0.9949
C 215.22 1 215.22 4079.97 <0.0001 – Adeq Precision 112.6789
D 51.54 1 51.54 977.03 <0.0001 – Std. Dev. 0.2297
AB 14.57 1 14.57 276.27 <0.0001 – Mean 92.53
AC 0.0138 1 0.0138 0.2617 0.6164 – C.V. % 0.2482
AD 124.16 1 124.16 2353.63 <0.0001 – – –
BC 10.03 1 10.03 190.20 <0.0001 – – –
BD 5.14 1 5.14 97.47 <0.0001 – – –
CD 24.23 1 24.23 459.35 <0.0001 – – –
A2 260.53 1 260.53 4938.96 <0.0001 – – –
B2 55.46 1 55.46 1051.39 <0.0001 – – –
C2 96.50 1 96.50 1829.43 <0.0001 – – –
D2 54.01 1 54.01 1023.84 <0.0001 – – –
Residual 0.7913 15 0.0528 – – – – –
Lack of Fit 0.7082 10 0.0708 4.26 0.0616 not significant – –
Pure Error 0.0831 5 0.0166 – – – – –
Cor Total 818.42 29 – – – – – –

Fig. 11. Diagnostic plots of (a) predicted versus actual conversion % of Karanja oil, (b) studentized residuals versus predicted conversion, (c) normal regression plot,
and (d) residual differences between predicted and actual conversion of experimental runs.

10
N. Ghosh et al.
Fig. 12. 3D surface diagram of Karanja oil biodiesel production efficiency based on the interaction of independent variables A-D.
was observed at 90 min, which declined due to reversibility in esterifi­
cation (Shu et al., 2010).
The relationship between temperature and catalyst loading is
depicted in Fig. 12c. Optimal conversion occurred at 55 ◦ C. The increase
in temperature initially resulted in more excellent conversion due to
esterification’s endothermic nature (Changmai et al., 2020, 2021).
Fig. 12d shows the correlation between the concentrations of MeOH
with reaction time. There was no improvement in conversion efficiency
at low methanol concentrations when the reaction time was increased
from 60 to 120 min. Despite the substantial variations, the maximum
conversion was at 50% w/w of MeOH concentration after 90 min, while
varying duration barely affected the results.
The interaction between temperature and MeOH concentration is
shown in Fig. 12e. With increasing concentrations of MeOH and
11
Journal of Cleaner Production 394 (2023) 136362
temperature, the FFA conversion also increased. 98.58% conversion is
reached at 55 ◦ C when the MeOH concentration was 50% w/w, after
which it declined. It can be explained by the fact that the reaction
mixture is diluted with (Juan et al., 2007) a large quantity of methanol,
thus introducing water and reinitiating the reaction (Zhang et al., 2014).
This reaction strongly depends on MeOH concentration and tempera­
ture, as shown in the 3D response curve.
The interaction between temperature and reaction time is depicted in
Fig. 12f. After 90 min at 55 ◦ C, conversion increased to 98.58%. As seen
in the 3D plot, significant interactions exist between the two factors.
Based on these findings, the ideal esterification reaction parameters
were determined to be 90 min of reaction time, 55 ◦ C of temperature, 4
wt % of catalyst loading, and 50% w/w of MeOH concentration.
N. Ghosh et al. Journal of Cleaner Production 394 (2023) 136362

3.6. Optimization of biodiesel yield observing the conversion at various time intervals t in Eq. (8).
− ln(1 − X) = kt (8)
In the present work, a numerical optimization approach also deter­
mined the optimal conditions for the four input parameters having a The activation energy was calculated using the Arrhenius equation
desirability function of 1. Optimizing FFA conversion within the study and k value at different temperatures (45–60 ◦ C), as shown in Eq. 9
variables’ lower and upper limits was the optimization strategy’s goal.
Ea
The RSM-CCD technique provided optimum conditions for the esterifi­ ln k = − + ln A (9)
RT
cation of Karanja oil with a catalyst loading of 4.025 wt%, methanol wt.
% of 54.43 wt%, a reaction time of 90.97 min, and a reaction temper­ Here, X = Karanja oil conversion to KOME, A = Arrhenius constant, Ea
ature of 56.2 ◦ C with an FFA conversion of 99.25 wt%. Average con­ = Activation energy, T = Reaction temperature, (K) and R = Universal
version of 97.68 wt % was determined using this condition in laboratory gas constant (8.314 × 10− 3 kJK− 1mol− 1).
trials conducted in triplicate, confirming that the developed regression A thermodynamic study of the esterification reaction was also con­
model is effective at explaining esterification. ducted to determine the impact of temperature on FFA conversion.
When determining whether a reaction is spontaneous or not, thermo­
3.7. Kinetics and thermodynamic study of the reaction dynamic parameters, including Gibbs free energy (G0), enthalpy (H0),
and entropy (S0), must be considered. As shown in Eq. (10), the Eyring-
The kinetic studies aimed to determine the order of kinetics during Polanyi relationship explains how thermodynamic parameters are
the esterification reaction. Maximum FFA conversion was obtained related.
when the temperature rose from the lowest level in the experimental k ΔS0 ΔH 0
( )
kb
matrix to the highest level. Esterification reaction follows pseudo-first- ln = − + ln (10)
T R RT h
order kinetics due to the surplus quantity of methanol, thus neglecting
the backward process. Based on this, we can express the reaction rate where kb = Boltzmann constant (1.38065 × 10− 23 J/K), and h =
(− rKO ) as follows: Planck’s constant (6.626 × 10− 34 J. s). Similarly, with the aid of ΔH0
− d[KO] and ΔS0 through Eq. (11), Gibbs’s free energy can also be calculated.
− rKO = = k[KO] (7)
dt ΔG0 = ΔH 0 − TΔS0 (11)
where k represents the rate constant of the reaction, [KO] is the con­ As demonstrated in Fig. 13a, the linear connections between –ln (1-
centration of Karanja oil and t is the reaction time. The rate constant, k, X) and time for reactions occurring between 45 ◦ C and 60 ◦ C support our
for the pseudo-first-order esterification of Karanja oil was determined by

Fig. 13. (a) Plot of –ln (1-X) vs time where X = Karanja oil conversion, (b) the corresponding plot of ln k vs 1/T, and (c) thermodynamic behaviour of esterifi­
cation reaction.

12
N. Ghosh et al. Journal of Cleaner Production 394 (2023) 136362

hypothesis that esterification followed pseudo-first-order kinetics (Chen commercial exploitation of the process by curtailing the overall pro­
et al., 2011). Substituting the rate constants in the Arrhenius equation duction cost of biodiesel. Hence, the judicious selection of waste pre­
(Eq. (9)) led to determining the esterification reaction’s activation en­ cursor materials copiously available in the nature for engineering
ergy (Ea.). An ln k vs T− 1 plot (Fig. 13b) is used to develop catalyst and producing biodiesel are very crucial as they offer definitive
pseudo-first-order kinetics. The pre-exponential factor and Ea for the advantages. The cost estimation towards catalyst preparation for the
reaction are deduced from the intercept and slope of the line (-Ea/R), current work presented here is advantageous for determining whether
respectively. From Fig. 13b Ea. was 62.61 kJ mol − 1, and the the method is suitable for practical use by considering all the criteria,
pre-exponential factor was 6.2 × 108 min− 1. At the same time, the slope viz., the source of the raw material, the method of production, the
and intercept of Fig. 13c are used to compute the values of ΔH0 and ΔS0. necessary treatment process, and especially reusability account for most
The change in enthalpy and entropy were 53.401 kJ/mol and – 0.1057 of the cost. The following observations, computed in US dollars ($), were
kJ/mol.K, respectively. The corresponding ΔG0 value is obtained by made while manufacturing one kg of sulfonated catalyst, as shown in
substituting ΔH0 and ΔS0 values in Eq. (11). Positive value of ΔH0 in­ Table 8.
dicates that the reaction is endothermic, whereas the negative value of According to the studies on reusability, the prepared catalyst can be
ΔS0 demonstrates the reaction is less disordered. The positive ΔG0 at all recycled three times, significantly reducing preparation costs. There­
the temperatures indicated that the reaction is non-spontaneous (Ani­ fore, for the current study, the cost of 1 kg acid-doped catalyst without
keev et al., 2012). reuse is approximately $49.498. After three reuses, the cost decreased to
around $16.49. Hence, 1 kg of sulfonated carbon catalyst can produce
3.8. Catalyst reusability studies nearly 100 kg of biodiesel, costing $0.1649 per kilogram. Reusability is
the only component contributing to this significant cost decrease. Recent
Heterogeneous catalyst synthesis is a complicated procedure that sources indicate that the commercially available activated char is about
requires a lot of physical work and numerous means for properly pre­ $14.5, which is far more expensive than the $2.562 we expended
paring the support and reagents for the catalyst synthesis. Therefore,
from an economic perspective, the catalytic base should be adequately Table 8
physically robust for repetitive doping to be effective while enduring Step-wise catalyst preparation costs.
degradation from the application. However, the catalyst’s functional
Step Description Amount
group needs to be properly doped for it to be useful for a few reap­
plications. In the current investigation, the reaction solution was filtered Cost of starting material (SMC) Waste material is locally available. $0
10% of the overhead cost for
to isolate the catalyst from it before being washed with acetone to
commercial production is
eliminate any leftover oil. The reaction mixture was evaporated at 90 ◦ C allocated to labour fees for
inside an oven to vaporize the residual acetone. The desiccated catalyst collection.
was then utilized for further catalytic reactions under predefined ideal Cost of size reduction (SRC) For batch studies, since reduction $0
was manual. 10% of overhead
circumstances with variable catalyst doses to evaluate the efficacy of the
costs are allocated for commercial
catalyst when reapplied. To verify the efficiency of the catalyst when manufacturing (machine
reused, the desiccated catalyst was then employed for further catalytic grinding).
conversions under defined ideal conditions with variable catalyst Cost of starting material washing HC = units consumed × unit cost $0.063
loading. The outcomes of the catalyst reusability experiment are pre­ = HC (heating cost) + WC for 1 L water
(washing cost) = 1 × $0.063
sented in Table 7. The catalyst displayed satisfactory catalytic activity
WC = 0 (cost already included
till three cycles, after which the reduction in biodiesel production was under HC)
observed. The main causes of ADC deactivation were the leaching of Drying cost of raw material (DRC) Time (h) × units consumed × cost $1.512
active sites (Azargohar and Dalai, 2008) and the methylation of sulfonic per unit
= 12 × 2 × $0.063
acid groups (Rokhum et al., 2022). Although the catalyst’s efficacy in
Carbonization cost (CC) = IEC IEC = N2 flow = $0.042 $0.609
catalyzing the esterification process was equivalent following perform­ (IEC = inert environment HC = Time (h) × units consumed
ing the doping process, the conversion of biodiesel dropped just creation costs) + HC (heating × cost per unit
marginally, demonstrating the operational durability of the catalyst cost) = 1.5 × 6 × $0.063 = $0.567
support and resilience to external loss from stirring. CC = $0.042 + $0.567
Activation costs (ANC) = SC SC = Time (h) × units used up × $0.441
(steam preparation cost) + HC cost per unit
3.9. Cost analysis for catalyst preparation (heating cost) = 1 × 1 × $0.063 = $0.063
HC = Time (h) × units used up ×
cost per unit
The productive and techno-economic commercialization of trans/ = 1.5 × 4 × $0.063 = $0.378
esterification process towards large scale biodiesel production signifi­ ANC = $0.063 + $0.378
cantly depends upon the efficacious performance and cost of the cata­ Therefore, raw material creation cost (RMC): $2.562
lyst. The costs associated with catalyst preparation and biodiesel CC + DRC + WC + SRC + SMC + ANC = $0.609 +$1.512+$0+ $0+
$0+ $0.441
production are essential to evaluate the feasibility of application po­
Impregnation cost (IC) = AGC AGC = Time (h) × units used up × $
tential of the catalyst and the product developed as well to mitigate the (agitation costs) + CCH (cost of cost per unit = (12 × 1 × $0.063) 42.436
ever-growing energy need. The efficiency of a spent catalyst for its chemicals) = $0.756
reusability in the successive cycles of operation also boosts the CCH = [amount of H2SO4 required
(in litre) × cost per litre] = 4 ×
$10.42 = $41.68
Table 7 IC = $0.756 + $41.68
Reusability of SC catalysts during esterification. Net cost involved RMC (raw material creation cost) $44.998
+ IC (impregnation cost) = $2.562
Sl No. Weight (%) Fresh First Second Third
+ $42.436
catalyst reuse reuse reuse
Total cost/kg = Net cost + running charges (10% $49.498
1 2 94.35 92.55 89.61 86.46 of the net cost) = $44.998 + $4.50
2 4 98.95 96.25 90.36 89.72 Final cost of 100 kg catalyst = one-time preparation cost/no. of $16.49
3 6 95.27 93.16 90.97 88.13 cycles towards catalyst reusability
4 8 95.31 94.26 91.04 88.11 = $49.498/3

13
N. Ghosh et al. Journal of Cleaner Production 394 (2023) 136362

Table 9 Table 11
Step-wise biodiesel preparation costs. Analysis of raw Karanja oil and KOME obtained.
Step Description Parameter Karanja oil KOME obtained Testing procedure

Total quantity of biodiesel production 100 kg Acid Value (mgKOH/g) 16.83 0.24 ASTM D974
Cost of Karanja oil $0.0 (feedstock was Free Fatty Acid (%) 8.46 0.11 –
obtained free of cost) Relative density (@25 ◦ C 0.88 0.815 ASTM D4253
Amount of catalyst required for 100 kg biodiesel 1 kg Kinematic viscosity (mm2/s) 24.73 2.5 ASTM D445
production Water content (%) 0.22 0.02 ASTM D3172
Cost of catalyst for 1 kg biodiesel $0.1649 (From Table 8) Calorific value (MJ/kg) 36.4 40.2 ASTM D6751
Methanol required for biodiesel production 40 kg Flash point (◦ C) – 165 ASTM 6450
Cost of methanol for 100 kg biodiesel production (40 × $0.47) = $18.8 Fire point (◦ C) – 176 ASTM 6450
(Quantity × price per kg of methanol) Cetane Number – 52.7 ASTM D613
Biodiesel production cost (time duration for (1.5 h × 45 × $0.051) = Aniline point (◦ C) – 51 ASTM D611
esterification (h) × units × per unit cost) $3.44 Ester content (%) – 96.9 EN14103
Additional expenses (washing cost + miscellaneous) $1.82
Cost of 100 kg biodiesel production ($0.164 +$18.8 + $3.44 +
$1.82) 4. Conclusion
= $24.224
Overhead cost (10% of net cost) $2.422
Total cost of 100 kg biodiesel production $24.224 + $2.422 =
The present study focuses on the development of an environmentally
$26.646 benign and cost-competitive contrivance for producing biodiesel from
Total cost of 1 kg biodiesel production $0.266 Karanja oil employing a sulfonated solid carbonaceous catalyst derived
from locally available wood apple shells. Under optimized reaction
conditions, RSM numerical optimization process predicted a conversion
preparing the activated char. The step-wise biodiesel preparation cost
of 97.68%. In contrast, methyl esterification of Karanja oil resulted in a
has been summarized in Table 9.
conversion of 98.95%, which is reportedly observed to be more
impressive than the previously reported works at comparatively less
3.10. Comparison of the present catalyst with the previously reported
reaction temperatures. Reaction time has the highest contribution to the
catalyst
FFA conversion, while the catalyst loading was found to be insignificant.
From the statistical analysis available from the ANOVA study, the model
According to previously reported studies, various heterogeneous
can optimize the process proficiently with accurate prediction. The
catalysts have been used to produce biodiesel. Table 10 summarizes the
legitimacy of the model is again confirmed by the experimental vali­
pertinent data for comparison with our designed catalyst, including
dation of the predicted optimum conditions, and the results acquired can
biodiesel production’s reaction conditions, feedstocks, and catalyst
be seen to be acceptable when compared to the predicted output.
types. In most cases, these processes worked well to convert the feed­
Additionally, the reusability of the spent catalyst was studied to check its
stock to FAME; however, drawbacks included elevated temperatures,
further application potential. Experiments on the reusability of the used-
high catalyst loadings, and longer reaction times. Biodiesel was obtained
up catalyst revealed an appreciable ester conversion of 86.46% after
with prolonged reaction times and temperatures for catalysts such as
three cycles. Kinetic studies showed that the esterification reaction for
Aminophosphonic acid resin D418 (Yin et al., 2012), NiHSiW/UiO-66
FFA conversion follows pseudo-first order kinetics with a very fast
(Zhang et al., 2020), [HMIM]HSO4 (Roman et al., 2019),
conversion rate of 6.2 × 108 min− 1 and activation energy of 62.61 kJ/
Fe3O4@SiO2– SO3H (Changmai et al., 2021), as reported in the litera­
mol, which signifies that the reaction occurs very vigorously with a
ture. Similarly, catalysts such as Oil cake waste-SO3H (Santos et al.,
minimum energy requirement. This implies that the process is cost-
2015) and [HMIM]HSO4 were utilized in large quantities to obtain a
effective in perspective of energy consumption, and optimized produc­
high conversion%. In light of the abovementioned viewpoints, the
tion could enhance the effectiveness of the process. The biodiesel ob­
catalyst provided here appears to be a good substitute for the previously
tained was subjected to GC-MS analysis to determine the compositional
reported catalysts.
percentages of the methyl esters obtained after esterification of the
Karanja oil, and the ester content found as per EN14103 standard of fuel
characterization was more than the minimum requirement of 96.4%.
Standard characterization experiments confirmed that the

Table 10
Comparison of the present catalyst with previously reported catalyst.
Sl. Feedstock Catalysts Alcohol to oil molar Catalyst loading Temperature Time Conversion/yield Reference
No ratio (wt. %) (◦ C) (h) %

1. JCO oil Fe3O4@SiO2– SO3H 9:1 8 80 3.5 98 Changmai et al.

(2021)
2. JCO oil Waste animal (Ox) bone 12:1 5 65 4 96.82 [55]
3. Oleic acid Aminophosphonic acid resin 14:1 10.2 115 10 92.02 [56]
D418
4. Oleic acid Oil cake waste-SO3H 12:1 20 60 2 94 [57]
5. Soybean ZIF-90-Gua 15:1 1 65 6 95.4 [58]
oil
6. Oleic acid NiHSiW/UiO-66 18:1 6 160 3 87.0 Zhang et al. (2020)
7. Oleic acid [HMIM]HSO4 15:1 14 110 8 95 Roman et al. (2019)
8. Karanja oil γ-alumina 9:1 1 50 50a 69.3 [59]
9. JCO oil Calcined oyster shells 9:1 5 65 180a 91.1 [60]
10. Karanja oil H2SO4 doped Limonia 50b 4 55 1.5 98.95 Present work
acidissima
a
Time (min).
b
Methanol weight %.

14
N. Ghosh et al.
physicochemical properties of the KOME produced fall within the
acceptable range of commercially useable biodiesel, being both low in
aromatic hydrocarbon content and stable with a high flash point and fire
point, making it suitable for storage and transportation. Cetane number
tests confirmed that the fuel is of acceptable quality for use as com­
mercial biodiesel with lower ignition delays than petro-diesel. Hence it
can be blended or used in its entirety as an alternative to petro-diesel.
According to the analysis of the costs involved in producing the cata­
lytic support, wood apple char produced locally is substantially less
expensive ($2.562) than activated carbon ($14.5) purchased from a
market, which offers a substantial route for commercialization on a
larger scale. The cost of biodiesel was estimated to be $0.266/kilogram,
which also indicates the higher chances of commercialization on an
industrial scale.
CRediT authorship contribution statement
Nabanita Ghosh: Conceptualization, Methodology, Investigation,
Writing – original draft. D. Rhithuparna: Formal analysis, Data cura­
tion, Software, Validation, Resources, Writing. Rexona Khatoon:
Formal analysis, Data curation. Samuel Lalthazuala Rokhum: Project
administration, Writing – review & editing. Gopinath Halder: Super­
vision, Project administration, Writing – review & editing.
Declaration of competing interest
The authors declare that they have no known competing financial
interests or personal relationships that could have appeared to influence
the work reported in this paper. The authors declare that there is no
conflict of interest.
Data availability
Data will be made available on request.
Acknowledgements
The funding from Department of Science and Technology, Govt. of
India vide project no EEQ/2021/000167 is appreciatively accredited.
The authors also acknowledge IIT Indore, IIT Madras and IIT Patna for
sample characterization.
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