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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.
* Corresponding author. Chemical Engineering Department, National Institute of Technology Durgapur, Mahatma Gandhi Avenue, Durgapur, 713209, West
Bengal, India.
E-mail addresses: [email protected] (N. Ghosh), [email protected] (D. Rhithuparna), [email protected] (R. Khatoon),
[email protected] (S.L. Rokhum), [email protected] (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
95% of the global feedstock utilized for biodiesel synthesis because they react with the catalyst, generating soap and water production during the
are simple to convert (Demirbas, 2009). The price growth of consumable saponification process. Thiruvengadaravi et al. used sulfonated zirconia
oils is mainly due to their extensive use in the manufacturing of fuels as a solid acid catalyst to esterify the high FFA Karanja oil. A reduction in
(Raj and Sahayaraj, 2010). Hence, researchers have recently employed acid value from 12.27 mg KOH/g to 1.3 mg KOH/g, confirming the
non-edible oils for biodiesel production, including Karanja, jatropha, conversion, was observed during this process (Thiruvengadaravi et al.,
and castor oil. The Karanja tree (Pongamia pinnata) is a medium-sized 2012). Similarly, Karmakar et al. converted FFA in Karanja oil using
evergreen tree belonging to the Leguminosae family, with an average sulfonated Delonix regia pods. A 99.86% FFA conversion was observed in
height of 12–15 m (Atabani et al., 2013; Bobade and Khyade, 2012). The the study (Karmakar et al., 2020a). Due to its many benefits, such as
large canopy and fragrant flowers make it an ideal plant for landscaping reusability, ease of separation, reduced corrosion, safety, time savings,
along highways. These trees can thrive in various soil types, including and cost, heterogeneous catalysts make it more economical and practical
sandy, rocky, and clayey, and are resistant to high saline conditions. to catalyze biodiesel production (Karmakar et al., 2020b). Zeolites,
Moreover, both their roots and canals prevent soil erosion. It takes metal oxides, and silica are readily available and used directly as het
Karanja 4–7 years to mature its fruits after it gets planted. The seeds are erogeneous catalysts (Narowska et al., 2019). In addition, certain
flat and elliptical, with a length of 3–6 cm and a width of 2–3 cm. The biomass-derived activated carbon such as paper sludge, flamboyant
reddish-brown seeds of Karanja fruits contain 1 or 2 kernels that pods (Dhawane et al., 2016a), fish scales (Chakraborty and Das, 2012),
resemble human kidneys. Approximately 30–40% of the oil content is and Mesua ferrea linn (MFL) (Bora et al., 2018) seed shells are func
present in the Karanja seed kernel, and nearly 900–9000 kg of oil gets tionalized and are employed as heterogeneous catalysts. Wood apple
produced per hectare. The bitter taste, dark brown color, and unpleasant fruit (Limonia acidissima) is a native crop of India, and its shells are
smell are the significant constraints of this oil for human consumption inexpensive and widely available (Chandrakala and Upadhyay, 2019).
(Bobade and Khyade, 2012). With an annual production of 13,500 The outcome of an experiment can be determined using batch studies
million tons, it is one of the most potentially valuable oils, but only 6% of by finding the correct range of parameter values. The reaction param
its oil is used (Khayoon et al., 2012). Compared with jatropha oil, Kar eters must be optimized to achieve the highest possible product yield. It
anja oil is more economical and emits fewer harmful substances (Karmee takes great time and energy to manually optimize one factor at a time
et al., 2004). It is most common for biodiesel to be produced with (OFAT). As a result, soft-computational methods are now employed for
methanol, although higher alcohols are preferred since they combine process optimization. These methods include Plackett-Burman design
better with oils during transesterification of triglycerides. However, the (PBD) or Taguchi OA (orthogonal array), which are factorial method
less polar alkyl groups in higher alcohols prevent them from reacting ologies illustrating a process’s individual effects on a given response
with the FFAs; hence methanol is often considered for FFA esterification. (Karmakar et al., 2021a, 2021b). At the same time, Box-Behnken design
Having high FFA content, Karanja oil is appropriate for biodiesel (BBD) and central composite design (CCD) are response surface meth
production using an acid catalyst by esterification. A large quantity of odologies (RSM) that use surface plots to illustrate interacting process
FFA in the feedstock can degrade the alkaline catalyst’s efficacy as they parameters (Karmakar et al., 2022). CCD and BBD cover a broader range
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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.
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N. Ghosh et al. Journal of Cleaner Production 394 (2023) 136362
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N. Ghosh et al. Journal of Cleaner Production 394 (2023) 136362
where, SSf = sum of squares of a particular factor, SSt = sum of squares direct measure of the conversion of FFA into FAME.
of the model.
3. Results and discussion
A round bottom flask with three mouths was utilized to esterify the The obtained catalyst was studied to define its physical qualities after
Karanja oil. A thermometer that quantifies the temperature of the re being wet impregnated with H2SO4 on the fabricated char made from
action mixture was attached to one of the flask’s three necks, a wood apple shells. After impregnating the H2SO4 on the carbonized
condenser was attached to the middle neck to help retain the methanol char, a substantial decline in surface area and pore volume was noticed,
in the system, and the remaining neck was used for the addition of the which was mostly due to the H2SO4’s good dispersion and adsorption on
catalyst inside the reaction mixture. The reflux condenser aids in the catalyst support. BET studies of activated char and ADC indicated
maintaining the methanol percentage considerably above the necessary surface area and pore volume. The results highlighted that: (a) activa
level stoichiometrically because methanol does not react in the reaction tion of the biochar with steam increases surface area by creating mi
mixture. The catalyst was added using the middle neck. After heating the cropores on the surface of the char, and (b) H2SO4 impregnation
required feedstock oil and methanol, the desired catalyst was added to drastically closes the pores of ADC. The pore volume and surface area for
the desired temperature. The stirring speed of 650 rpm was considered activated char are 0.0704 cm3/g and 321.52 m2/g, respectively, ac
optimum while working with Karanja oil and methanol using acid-based cording to BET data, whereas these values are 0.3126 cm3/g and 807.4
esterification. Therefore, it was set constant for this optimization study. m2/g for ADC. The presence of doped sulfur in the prepared catalyst can
Apart from stirring speed, other reaction parameters were varied to get be confirmed by EDAX analysis. The elemental structure for the acti
an optimized design matrix, including each set’s optimum parametric vated catalyst is shown in Fig. 4a, where sulfur is present in insignificant
ratios performed to get experimental results. After the reaction, the amounts in the activated char catalyst accounting for only 1%. Never
mixture was cooled to ambient temperature to halt additional conver theless, the doped resulted catalyst is perceived to be C = 21%, O = 24%,
sion. After that, the catalyst was separated using filtration, and methanol S = 51%, Na = 1%, K = 1% and Ca = 1% as shown in Fig. 4b (Karmakar
was then retrieved utilizing distillation by a rotary evaporator. In order et al., 2020a; Show et al., 2022). It is evident in the SEM micrographs
to get rid of contaminants and eluted acidic functional groups, the that have been provided for both sulfonated carbon and steam-activated
esterified oil must be rinsed with water. The esterified oil was then carbon. According to Fig. 5a, the catalyst support features a surface
poured into a separatory funnel after being washed until the water’s pH structure that can adsorb functional groups as a result of the passage of
was neutral. The oil sample was ultra-centrifuged before this step to steam. This indicates that the activation process followed by super
eliminate more contaminants. The FAME yield of the esterified oil was heated steam could completely modify the char’s surface characteristics
measured by titration analysis that identifies the FFA percentage as a by generating pores. As further evidenced by Fig. 5b, catalytic functional
Fig. 4. (a) EDAX spectral analysis of steam-activated catalyst. (b) EDAX spectral analysis of H2SO4 impregnated catalyst.
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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 3.2. Fuel characterization
fonated carbon support, resulting in surface smoothening and pore
plugging. Fig. 6 depicts the FTIR data for steam-activated and sulfonated To determine the formation and chemical structure of the synthe
carbon catalysts after acid impregnation. The appearance of peaks at sized KOME, 1H NMR and 13C NMR (Nuclear magnetic resonance) were
various characteristic wavenumbers are as follows for activated carbon: performed on (AVNACE NEO500, Switzerland) series instrument with a
940 cm− 1 explains the presence of single bond C–H alkene stretches, spectrometer frequency of 500 MHz. GC-MS was used to investigate the
1526 cm− 1 shows the presence of C–C stretch, 1680 cm− 1, and 1692 chemical composition of the synthesized KOME. GC-MS was performed
cm− 1 represents C– – C alkene stretches of weak and medium bond on Agilent Model 8890 instrument equipped with Single Quadrupole
strength respectively, For the sulfonated carbon, following peaks were Mass Spectrometer (5877 B MSD) analyzer. (FTIR), Fourier transform
observed: 1102 cm− 1 is characteristic of the sulfoxide group, while the infrared spectrometer was utilized to confirm the presence of ester
very sharp peak at 1158 cm− 1 confirms the presence of the H2SO4 content (FTIR C109292, spectrometer USA).
adsorption on the carbon support. Fig. 7 depicts the XRD analysis, which After the completion of the esterification reaction, the produced
helps understand the samples’ amorphous structure. From the graph, as KOME was checked by performing 1H NMR and 13C NMR analysis and
shown in Fig. 7a, it is seen that characteristic peaks observed for ADC was compared with raw Karanja oil, as shown in Fig. 8. Fig. 8a repre
indicate proper sulfonation. The diffraction peaks are identified using a sents the 1H NMR spectrum of FAME. The appearance of a peak at 3.66
standard JCPDS library (Thiruvengadaravi et al., 2012). Fig. 7 shows the ppm confirms the formation of FAME (Fig. 8a). The singlet peak at 3.66
presence of different peaks specific for each sample: activated carbon ppm represents the methoxy protons of FAME, and the triplet peak at
and doped carbon can be seen at 24.994◦ and 40.89◦ , which confirms 2.31 ppm can be attributed to α− CH2 protons. Raw Karanja oil and
that the support is carbonaceous in nature. The curve for the ADC synthesized KOME have different NMR spectra, as evidenced by the lack
catalyst shows broad peaks in the range between 15◦ and 25◦ and be of methoxy protons at 3.6 ppm in raw oil (Fig. 8c), indicating that
tween 35◦ and 45◦ , which are indicative of proper H2SO4 that have Karanja oil has been converted to KOME. From 13C NMR, the appearance
shown similarity with some of the peaks obtained from the standard of peaks at 51.5 ppm for the –OCH3 group (Fig. 8b), carboxyl peaks
dimethyl sulfate. These have been marked in Fig. 7 (24.484◦ , 25.56◦ , around at 174.49 and 176.87 ppm, olefinic carbons at 127–130 ppm
40.88◦ ) along with the planes (131, 003 and 511, respectively). (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
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N. Ghosh et al. Journal of Cleaner Production 394 (2023) 136362
Fig. 7. XRD plot of (a) steam-activated wood apple shell and (b) sulfonated wood apple shell after H2SO4 doping.
cm− 1. 3.3. Modelling and analysis of data using response surface methodology
As shown in Table 11, the fuel qualities are found to be within (RSM)
acceptable commercial standards for biodiesel by ASTM characteriza
tion testing. After esterification, the product has a very low kinematic Optimization of the esterification reaction was carried out with the
viscosity (KV), which indicates favorable flow characteristics and ease of experimental matrix of the RSM central composite design (CCD). Ac
atomization during the injection. Adequately high cetane number of a cording to experimental runs, biodiesel conversion ranged from 80.96 to
fuel indicates good quality, while its higher aniline point indicates that it 98.95%. Table 4 displays the actual and predicted result for each
is paraffin-rich and has clean-burning properties. The fuel’s high flash experimental run. Meanwhile, the coded factors A-D influence the bio
and fire points signify the sample’s high thermal stability. The fuel’s diesel yield, as described in Eq. 6
high calorific value indicates that it also has a high energy content.
Biodiesel yield (Y) = 98.75–0.2863A + 0.9204B + 2.99C + 1.47D - 0.9544
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 AB - 0.0294 AC − 2.79AD - 0.7919BC + 0.5669BD − 1.23CD - 3.08A2
-1.42B2 -1.88C2 -1.40D2 (6)
components.
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N. Ghosh et al. Journal of Cleaner Production 394 (2023) 136362
3.4. Statistical analysis through ANOVA Experimental conversion of Karanja oil to KOME was evaluated using
3D response surface plots (Fig. 12) to determine the influence of inde
As shown in Table 6, the outcomes of the experimental runs are pendent parameters A-D (A = catalyst loading, B = methanol (MeOH)
analyzed and summarized using statistical analyses of variance concentration, C = reaction time, and D = reaction temperature)
(ANOVA). F-value (Fischer’s exact test) for the regression model (Sharma et al., 2019). Fig. 12a illustrates how the concentrations of the
developed was high enough to indicate the significance of the model. A catalyst and MeOH affect conversion. The conversion increased with
p-value <0.0001 implies that there is only a 0.01% possibility that the increasing catalyst and MeOH concentration to reach its maximum at 4
values in the proposed model were acquired by chance, along with the wt% and 50% (w/w), respectively. Since esterification is reversible,
high F-value, providing further assurance that the results were error-free extending the reaction conditions beyond the optimum value can
(Mukherjee et al., 2020). Additionally, the R2 values for predicted and moderately reduce conversion. When added more than necessary,
adjusted data (0.9949 and 0.9981, respectively) differed by less than MeOH dilutes the system, impairing conversion rates and reactant in
0.2, as seen in the model comparison and fit statistics, demonstrating a teractions. Low quantities of MeOH, in contrast, are inadequate to stop a
strong connection between experimental and theoretical data. This led backward reaction (Ramachandran et al., 2011). Similarly, this study
to the inference that the selected model could be utilized to explore the maintained the catalyst concentration between 2 and 6% w/w, with 4%
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N. Ghosh et al. Journal of Cleaner Production 394 (2023) 136362
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) % %
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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
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.
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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 temperature, the FFA conversion also increased. 98.58% conversion is
cation (Shu et al., 2010). reached at 55 ◦ C when the MeOH concentration was 50% w/w, after
The relationship between temperature and catalyst loading is which it declined. It can be explained by the fact that the reaction
depicted in Fig. 12c. Optimal conversion occurred at 55 ◦ C. The increase mixture is diluted with (Juan et al., 2007) a large quantity of methanol,
in temperature initially resulted in more excellent conversion due to thus introducing water and reinitiating the reaction (Zhang et al., 2014).
esterification’s endothermic nature (Changmai et al., 2020, 2021). This reaction strongly depends on MeOH concentration and tempera
Fig. 12d shows the correlation between the concentrations of MeOH ture, as shown in the 3D response curve.
with reaction time. There was no improvement in conversion efficiency The interaction between temperature and reaction time is depicted in
at low methanol concentrations when the reaction time was increased Fig. 12f. After 90 min at 55 ◦ C, conversion increased to 98.58%. As seen
from 60 to 120 min. Despite the substantial variations, the maximum in the 3D plot, significant interactions exist between the two factors.
conversion was at 50% w/w of MeOH concentration after 90 min, while Based on these findings, the ideal esterification reaction parameters
varying duration barely affected the results. were determined to be 90 min of reaction time, 55 ◦ C of temperature, 4
The interaction between temperature and MeOH concentration is wt % of catalyst loading, and 50% w/w of MeOH concentration.
shown in Fig. 12e. With increasing concentrations of MeOH and
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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.
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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) %
14
N. Ghosh et al. Journal of Cleaner Production 394 (2023) 136362
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