Journal of Cleaner Production 255 (2020) 120313

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Journal of Cleaner Production

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

Delonix regia heterogeneous catalyzed two-step biodiesel production

from Pongamia pinnata oil using methanol and 2-propanol
Bisheswar Karmakar , Sucharita Samanta , Gopinath Halder *
Department of Chemical Engineering, National Institute of Technology, Durgapur, India

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

Article history: The study described here was focussed on preparing heterogeneous catalysts (acid and base) by H2SO4
Received 4 September 2019 and KOH wet impregnation technique from raw Delonix regia pods after carbonization and steam acti-
Received in revised form vation, which was used in converting free fatty acids and glycerides in karanja oil into fuel-grade esters.
29 December 2019
Resistance to thermal degradation of the precursor material was evaluated by TGA analysis, while
Accepted 28 January 2020
catalyst characterization was done through BET, EDAX, FT-IR, SEM and XRD. These helped in estimating
Available online 29 January 2020
efficient surface modification and efficient doping of functional groups. Optimization of both esterifi-
Handling editor: Jun Bi cation and transesterification steps is done through L16 Taguchi matrices, with the following process
parameters: agitation speed, alcohol to oil ratio, catalyst concentration, reaction duration, reaction
Keywords: temperature. With a maximum FFA conversion of 99.86%, the biodiesel yield was 99.39%. Fuel charac-
Biodiesel production terization tests and GC analyses for residual glycerides showed that the fuel has acceptable physico-
Catalyst reusability chemical properties according to ASTM standards with low residual glycerides. Catalysts show signifi-
Delonix regia cant reusability with sulfonated (H2SO4 impregnated) catalyst retaining efficiency up to 3 uses and base
Heterogeneous two-step production
catalyst (KOH doped) up to 7 uses. A cost analysis of catalyst preparation shows that the indigenously
Pongamia pinnata
developed catalysts reduce production costs by a significant margin, proving to be lucrative for
Taguchi L16
commercialization.
© 2020 Elsevier Ltd. All rights reserved.

1. Introduction and transesterification with acids, bases or enzymes (biocatalysts).

Biodiesel being one of the renewable, biodegradable alterna-
tives to fossil energy, researchers made use of various edible and
non-edible oils from plants as well as waste oils and animal fats
over a wide range of approaches for the development of commer-
cially usable biodiesel (AI-Nimr and AI-Dafaie, 2014; Magno et al.,
2015; Ramkumar and Kirubakaran, 2016). In addition to being
physico-chemically similar to petro-diesel and being compatible
with diesel engines, biodiesel has the advantages of having higher
thermal stability, proving to be safer for transportation. Due to low
sulphur content, greenhouse gas emissions are also lower. The
range of feedstock available as well as the techniques that are
available for exploitation in the field of biodiesel production are
wide. The production of fuel-grade esters from free fatty acids and
glycerides (mono-, di- and tri-) involves esterification with acids
* Corresponding author. Department of Chemical Engineering, National Institute
of Technology Durgapur, M.G. Avenue, Durgapur, 713209, West Bengal, India.
E-mail addresses: bk18gene@gmail.com (B. Karmakar), sucharita.samanta111@
gmail.com (S. Samanta), gopinath.halder@che.nitdgp.ac.in (G. Halder).
Edible oils are not used to avoid straining food sources. Animal fats
are hard to process and are still used in skincare products due to
their long shelf life. Oils from non-edible plants like karanja (Pon-
gamia pinnata), Croton megalocarpus, physic nut (Jatropha curcas),
rubber seed (Hevea brasiliensis), mahua (Madhuca indica), castor
(Ricinus communis), etc. can be grown in relatively harsh climatic
conditions and in areas that are either unsuitable for food crop
production or for decorative purposes. From the family Legumi-
naceae, karanja (Pongamia pinnata) grown in India, is a glabrous
tree of medium size that can grow in tidal forests, coastal areas,
riverbanks and even roadsides (Sharma and Singh, 2008), making
production of biodiesel feasible. The increased viscosity of oils is
primarily because of glycerides (mono-, di- and tri-) being present
in large quantities and thus transesterification with alcohols is
needed to convert these glycerides into their alkyl esters that have
diesel-like properties (Sharma and Singh, 2008). Oils with high FFA
(free fatty acid) content or traces of water in them cannot be base
transesterified because saponification occurs with the FFA, while
presence of water causes hydrolysis of triglycerides into FFA
(Karmakar and Halder, 2019). Therefore, such oils need to be

https://doi.org/10.1016/j.jclepro.2020.120313
0959-6526/© 2020 Elsevier Ltd. All rights reserved.
2 B. Karmakar et al. / Journal of Cleaner Production 255 (2020) 120313
converted into their esters through a two-step mechanism that
involves FFA esterification (acid catalyst) and subsequent glyceride
transesterification (base catalyst) to yield the final product.
Over the past few years, many researchers have made use of a
wide range of feedstock for biodiesel production using a myriad of
catalysed approaches. These approaches have centred on using
homogeneous or heterogeneous catalysts, with many researchers
opting to use inert supports to dope functional groups such as acid
or base groups or even heavy metals that can act as a catalyst in a
transesterification. While some relied on acid or base single step
conversions, some others have utilized transition metals doped on
inert carbonaceous supports as catalysts. Karmakar et al. and
Dhawane et al. used H2SO4 in a homogeneous system for conver-
sion of castor oil and waste cooking oil into biodiesel with 90.38%
and 95.376% yield, respectively (Karmakar et al., 2018; Dhawane
et al., 2018). High FFA (~15% w/w) Calophyllum inophyllum oil was
converted by Dawodu et al. in a single step using methanol with
carbonized C. inophyllum cake which were HSO3 doped, resulting in
around 99% w/w yield of fuel (Dawodu et al., 2014). Biodiesel had
also been prepared from Mesua ferrea linn (MFL) seed oil with
methanol using carbonized MFL seed shells impregnated with
H2SO4 which resulted in a 95.57% yield of fuel (Bora et al., 2018).
Also, another work has been reported by Karmakar et al. which
involved using carbonized and H2SO4 doped Delonix regia pods,
which was used to obtain a 97.04% yield from high-FFA Madhuca
indica oil using methanol (Karmakar et al., 2020). In primarily base
catalysed approaches involving oils with negligible FFA or pre-
treated oils free of FFA, some works have also been reported.
Dhawane et al. had previously reported in separate works of con-
verting rubber seed oil into biodiesel; carbonized Delonix regia char
was separately used after impregnation with KOH or Fe(II) along
with methanol. The biodiesel yields were: 96.31% for Fe(II) doped
carbon (Dhawane et al., 2016b) and 89.81% for KOH doped carbon
(Dhawane et al. 2016a). Homogeneous CaO catalyst developed from
calcined chicken manure was used in the transesterification of
waste cooking oil using methanol with over 90% FAME yield
(Maneerung et al., 2016).
The ‘one-variable-at-a-time’ (OVAT) approach is an optimiza-
tion technique needing a large number of experiments. This makes
the process both wasteful and costly, since it is laborious, time-
consuming and unnecessarily repetitive. Hence, software guided
approaches such as Factorial and Response Surface Methodology
(RSM) are preferable that provide outputs based on mathematical
models. Backed with statistical analysis, the optimum levels for a
given set of reaction parameters can be evaluated very precisely.
Being a factorial approach, the Taguchi OA can incorporate higher
number of process parameters with very less number of resulting
runs and the data fed as a response is sufficient in predicting the
optimum reaction conditions. Thus for the present approach
Taguchi L16 matrix was used for optimization of the two-step
process.
The present study provides insight into a novel approach uti-
lizing a dual step conversion of karanja oil that attempted to and
was successful in converting FFAs using acid esterification and
glycerides (mono-, di- and tri) using base transesterification for
biodiesel synthesis. For the first time, instead of methanol, 2-
propanol was used as a better reactant (due to its low polarity
resulting in better miscibility with the oil) during the base cata-
lysed conversion. Additionally, the catalysts developed were based
on a carbonaceous support that is inert in nature, as well as reus-
able as discussed later. Raw Delonix regia (flamboyant) pods were
collected and used as the precursor material for developing a car-
bon support. The raw material is evaluated by thermo-gravimetric
(TGA) analysis for ascertaining optimal carbonization temperature
and then carbonized accordingly, followed by physical (steam
activation) to enhance surface properties. Both the acid and base
catalysts are made by wet impregnation of H2SO4 and KOH
respectively. Characterization of the steam activated char and the
wet impregnated char (both acid and base type) is done to deter-
mine changes before and after modification. The surface modifi-
cation is analysed by scanning electron microscopy (SEM), analysis
of elemental composition by EDAX (energy dispersive X-ray spec-
troscopy), presence of functional groups by FT-IR (Fourier Trans-
form Infrared Spectroscopy) and XRD (X-ray Diffraction) analysis,
modification of porosity and surface area by functional group
impregnation using BET (BrunauereEmmetteTeller) analysis. The
first step is acid esterification of FFA in the presence of methanol to
form FAME. The esterified oil, free of FFA is then base transesterified
using KOH-impregnated char in the presence of 2-propanol. Both
processes are optimized using L16 Taguchi orthogonal array (OA)
approach. Fuel characterization tests conducted show whether the
product obtained meets the standard criteria to be used as a fuel.
Both the catalysts are studied for their reusability and the cost of
preparation was estimated to determine if the developed process
can be scaled up for commercial level biodiesel production. During
scale-up, it can be expected that the cost of oil procurement from
local mills would be constant. Since catalyst costs are expected to
be high due to the use of laboratory grade reagents, the reusability
of these catalysts is of huge benefit to the applicability of this
process on a commercial level. Since industrial grade chemicals are
far cheaper compared to the laboratory grade chemicals used in this
study, the large scale production costs, when computed, are ex-
pected to be much lower than computed here.
2. Materials and procedure
2.1. Materials required
For the preparation of the heterogeneous catalysts, raw Delonix
regia pods were collected from the local areas both within and
around the institute campus at Durgapur, West Bengal, India. Kar-
anja oil was obtained from a local oil mill. The oil was freed of re-
sidual water and impurities by heating above 80
C and filtration
respectively. For the study, reagents of analytical grade were uti-
lized. For the acid esterification, methanol (99.50%; Merck, India)
was preferred due to its low boiling point as well as its low carbon
chain length compared to 2-propanol (99.50%, Merck, India) which
as used for the base transesterification due to high miscibility of
branched chain alcohols with the oil. Concentrated H2SO4 of min.
98% strength is used for the sulfonation of the carbon support to
develop the acid catalyst while KOH is used for the development of
the base catalyst by wet impregnation process as well as a titration
standard for the determination of FFA in both the oil and the acid
esterified product. For FFA estimation, 2-propanol is also used with
phenolphthalein as the end point indicator. Arium-611 DI ultra-
pure water system (Sartorius A.G., Gottingen, Germany) was used
to get deionized water used throughout the experiments.
2.2. Preparation of heterogeneous catalyst
The accrued flamboyant pods were cleaned by water for
removing dust particles as well as other impurities. Thereafter, they
were subjected to additional cleaning by deionised water for
removing residual ions, after which they were dried in a hot air
oven; this removes the moisture. The pods were ground for size
reduction, and subsequently carbonized in a muffle furnace
(CSMF136Z, N.R. Enterprise, Kolkata, India). The carbonization
temperature was determined prior to the process by TGA of the raw
pods to determine the temperature at which the mass loss was
negligible resulting in a steady residual mass. The obtained
 B. Karmakar et al. / Journal of Cleaner Production 255 (2020) 120313
temperature used for carbonization was thus 500
C with contin-
uous flow of N2 for 1 h. The carbonized pods need physical acti-
vation for enhancement of surface properties and therefore steam
was passed under 1.5e2 kg/cm2 at 350
C for 1.5 h (Dhawane et al.,
2015). This enhancement enables the inert carbon support to
display better adsorption properties during the wet impregnation
of both H2SO4 and KOH and is dubbed as ‘activated carbon (AC)’. For
H2SO4 impregnation, the AC was ‘sulfonated’ as follows: 40 ml of
conc. H2SO4 (98% min.) was loaded with 5 g of AC and run at 120
C
for 10h under 550 rpm agitation12. In order for KOH impregnation
onto the surface of the AC, a 10N aqueous solution of KOH was
prepared and 20g of AC was loaded onto 200 ml of the 10N solution.
The mixture thus obtained was then kept in an incubator at 30
C
under orbital shaking at 200 rpm for 24 h (Dhawane et al., 2016a).
For removal of the excess H2SO4 or KOH from their respective
mixtures, the prepared catalysts were repeatedly washed using
deionized water and filtered, then dried. This results in the
obtainment of acid and base heterogeneous catalysts that has a
carbonaceous, inert support with high thermal resistance.
2.3. Characterization of raw pod and developed catalysts
Initial TGA analysis of the pods establishes the percentage of
non-volatile components in the raw material and the carbonization
temperature. For TGA analysis, an instrument DTG-60H, synchro-
nized DTA-TG apparatus (Shimadzu, model C30574700290, Japan)
was used. TGA was performed under 30
to 700
C temperature
range with 10
C/min increment, N2 based purging at 19.8 ml/min
(flow rate). For studying the modification in surface properties after
steam activation and H2SO4 or KOH impregnation, the 3 types of
Delonix regia char were characterized using a SEM (JEOL JSM- 6030,
India) and to identify incorporation of specific functional groups on
the samples, FT-IR was used. BET analysis identifies each sample’s
physical properties by estimating its pore volume and surface area
using an instrument Smart Sorb 92e93 (Smart Instruments, India).
The operating temperature was maintained at 77K and surface
properties were estimated by N2 desorption-adsorption method.
An X-ray Diffractometer (D8 ADVANCE BRUKER AXS, Germany) is
used for XRD analysis. It is useful in obtaining the crystalline
structure of a given sample, such as before and after functional
group impregnation; such changes in the crystalline structure are
recorded as distinctive ‘peaks’ (in the plot). Parallel beam Cu Ka
radiation was used over a 10e50
2q range, with 0.02 step size and
results obtained were compared with JSDPS standard library. To
detect inorganic elements, an EDAX instrument (OXFORD INCAX-
sight) was used.
2.4. Preliminary analysis of oil
Pongamia pinnata oil needed to be characterized via standard
ASTM tests for insight into its properties. Physico-chemical traits
like kinematic viscosity, relative density, water content, calorific
value as well as acid value (corresponding to FFA content) were
tested. Relative density is presented as mass per unit volume of
sample relative to that of water. Kinematic viscosity (KV) of the oil
was estimated using a redwood viscometer following standardized
ASTM D445 testing procedure which measures the time taken by a
fixed amount of oil to flow through an orifice at a certain temper-
ature. The KV can differ based on the temperature. The weights of
the oil before and after drying at 80
C were considered and
computed for difference, presented as moisture/water content.
Calorific value of the sample is estimated using a bomb calorimeter
(Parr 1672 calorimetric thermometer). The sample is loaded into
the bomb and then combustion of the sample aided by O2 supply
leads to a temperature change in the surrounding water bath,
3
which is calibrated to provide an output of energy contained per
unit mass of sample. The estimation of AV and FFA involves the
titration of a specific quantity of sample dissolved in 10 ml of 2-
propanol against KOH solution of specific strength, while the end
point indicator used was phenolphthalein (Karmakar et al., 2020).
Estimation was done in triplicates and the mean value was
considered. Eqs. (1) and (2) are used to calculate FFA content and
AV:
28:2  N  t
FFA% ¼ (1)
m
56:1  N  t
AV ¼ (2)
m
Here, 28.2 is the standard weight taken for oleic acid, 56.1 is
molar weight of KOH, titre value is denoted by t, N is the strength of
KOH solution (expressed in normality), m is the mass of oil used
(Karmakar et al., 2018).
2.5. Design of experiments (DOE) for optimization
For both the acid esterification and base transesterification
steps, five reaction parameters need to be optimized for maximum
FFA conversion or biodiesel yield and therefore the Taguchi
orthogonal array (OA) design devised by Dr. Genichi Taguchi is the
preferred approach. This technique relies on a statistical prediction
that elucidates the optimum conditions of every process parameter
based on the mean and variance of every output generated (Sathish
Kumar et al., 2015). The results are in the form of individual para-
metric effect on product yield and all other parameters are retained
at baseline levels. From Eq. (1), an N number of experiments are
required, relying on P number of experimental parameters, while L
number of levels for each chosen parameter in a relation as given in
Eq. (3):
N ¼ (L - 1) P þ 1 (3)
Based on this, the L16 OA chosen gives a total of only 16 runs for
4 levels of each of the five process parameters. The parameters
chosen were agitation speed, catalyst concentration, alcohol
(methanol/2-propanol) to oil ratio, reaction temperature and re-
action time. (Tables S1 and S2). Design Expert software version
11.0.0.1 was used for developing the matrix and evaluating the
results.
2.6. Two-step fuel production
The reactor used for the present study was a flat bottom, 3
necked flask of 2 L capacity. The side necks were fitted with a
thermometer and a reflux condenser. The heating and stirring of
the reaction mixture is by means of a hotplate magnetic stirrer,
allowing alteration of both plate temperature and rpm. The reactor
is charged with a fixed amount of sample (oil or esterified oil), to
which a recommended quantity of alcohol is added followed by the
required amount of heterogeneous catalyst (acid/base) after the
desired temperature is reached. The mixture is cooled to below
20
C to quench the reaction. After filtration, the catalyst is washed
and kept for reusability tests, while the mixture is heated for
alcohol recovery and then left in a separating funnel for the sepa-
ration of water (formed from acid esterification), glycerol and im-
purities. The product is washed with water to remove leached
acidic or basic functional groups before being subjected to standard
ASTM tests for characterization.
4 B. Karmakar et al. / Journal of Cleaner Production 255 (2020) 120313

2.7. Empirical model equation and analysis of variance (ANOVA)
The mean response compared to SD is the basis for calculating
the signal to noise ratio (SNR) and optimize the process. However,
for elucidation of the effect of discrete reaction parameter on re-
sponses, a statistical ANOVA (analysis of variance) is done (Kumar
et al., 2015). Then, the influence of every reaction variable that is
deemed significant in the processes is represented as sum of
squares (SS) value, and can be converted into individual contribu-
tion% based on Eq. (4):
SSf
% contribution of factor ¼  100
SST
In this equation, the sum of squares of a particular factor is
denoted by SSf while the sum of squares of the model is denoted as
SST, the total. A regression equation developed by using the fed data
can then be confirmed for accuracy by conducting experiments
under optimal conditions predicted.
2.8. Fuel characterization
For the estimation of physico-chemical traits, both the esterified
oil as well as transesterified biodiesel were analysed by standard
ASTM tests. Viscosity (using Redwood viscometer) of a fuel is an
indication of the ease with which it can be atomized by spraying for
combustion in an engine. At flash point, the fuel generates ignitable
vapours enough for a brief flash, while at a relatively higher tem-
perature the vapours formed are sufficient enough for sustaining a
flame. A Pensky Martens apparatus (closed cup) was used for the
measurement of fire and flash point. Sample is charged into the
chamber of the apparatus and a flame injector can be rotated such
that it dips into the chamber for ignition. When the temperature is
sufficient for vapour formation, upon introduction of the flame, the
vapour mixture spontaneously ignites giving either a brief flash or a
continuous flame for about 10 s. Higher values are indicative of
thermal stability, thereby storage and transportation of the fuel are
easy (Canoira et al., 2010). Acid value and FFA% can be estimated
using a titrimetric assay as discussed in Section 2.4. (Dhawane et al.,
2015). Measurement of aniline point of the biodiesel gives an es-
timate of the aromatic hydrocarbon content, such as paraffins, and
higher is preferable. Cetane number and calorific value are also
important quality parameters for the product obtained. The fuel is
also visually checked for cloudiness, which is observed due to the
presence of moisture.
3. Results and discussion
3.1. Analysis of raw materials
The fatty acid profile of karanja oil is presented in Table 1. Pre-
liminary analysis of the Pongamia pinnata oil was performed for
establishing the physical and chemical properties, listed in Table 6.
Water content of the oil is low; but a high kinematic viscosity of
Table 1
Fatty acid compositional profile of Karanja oil.
24.71 mm2/s was noted which is typical of bio-oils and therefore
cannot be used directly as fuel in diesel engines. High calorific value
noted can be considered favourable towards expectations of energy
rich esters after transesterification. FFA and AV are high (8.46% w/w
and 16.83 mg KOH/g), hence acid esterification (pre-treatment) of
the oil is necessary (Karmakar and Halder, 2019).
Table 2 summarizes the raw flamboyant pod proximate analysis
results, which reveal a significant amount of fixed carbon content
(46.89%) which is economical enough for developing a porous inert
carbonaceous support, proving the chosen precursor material to be
suitable for H2SO4 or KOH impregnation. Thermal stability of the
pods was determined using thermo-gravimetric analysis (TGA).
(4)
From Fig. 1 it is clear that all of the volatile matter is lost when the
temperature is raised up to 500
C. Further rise in temperature till
700
C does not affect the mass loss considerably, and the residual
mass is constant at around 54%. Therefore, the carbonization tem-
perature is set at 500
C (Dhawane et al., 2017). The derivative of
weight loss percentage derived from the TGA data is plotted as a
DTG (Derivative of Thermo-gravimetry) curve and the increase in
thermal degradation (dW/dt) is seen to be occurring in 2 phases,
the first being a curve above 60
C that corresponds to loss of water
molecules which occurs up to 150e220
C (Chaudhary et al., 2016).
With further rise in temperature, the other peak noted between
300
and 500
C is due to the loss of volatile organic components
(VOCs) (Karmakar et al., 2020). It is also seen from separate TGA
plots of the steam activated carbon as well as the H2SO4 doped acid
catalyst and the KOH doped base catalyst that there is practically no
mass loss for the entire selected temperature range. This shows the
efficiency of carbonization as well as the thermal stability of pre-
pared catalyst. Therefore, the Delonix regia char once prepared and
steam activated, can be used for a long time for development of
both acid and base catalysts.
3.2. Characterization of catalysts
The activated, sulfonated and KOH impregnated carbon were
subjected to BET analysis in order to analyse their pore volume and
surface area, the results of which are as follows: AC has a pore
volume ¼ 0.3246 cm3/g and surface area ¼ 811.5 m2/g while pore
volume and surface area for SC are 0.0721 cm3/g and 330.62 m2/g
respectively; the KOH doped carbon (KC) has a pore
volume ¼ 0.0263 cm3/g and surface area ¼ 215.38 m2/g. A change in
surface area with a corresponding decrease in pore volume is seen
in both the catalysts developed implying effective doping of the
carbon support by H2SO4 and KOH. This can be further confirmed
by the SEM images shown in Fig. 2a-d. From Fig. 2a, it is seen that
the carbonized char has a surface that is extremely rough in
appearance with ridges and a poorly formed porous structure
varying in size, which are modified and mostly enlarged after
activation by steam as seen in Fig. 2b. Fig. 2c shows that H2SO4
doping effectively blocks the pores due to proper doping of H2SO4
on the surface of the char. This results in an effective acid catalyst. A
similar observation is noted for Fig. 2d, where KOH doping has a
similar effect on the surface morphology of the carbon support.
EDAX analysis of the synthesized catalysts showed the presence of
different elements in the prepared catalysts. For the sulfonated

Fatty acid Chemical name Formula Structure Weight% Table 2

Palmitic Hexadecanoic C16H32O2 16:0 10e11 Proximate analysis of raw Delonix regia.
Stearic Octadecanoic C18H36O2 18:0 6e7
Content name Percentage
Oleic Cis-9-octadecenoic C18H34O2 18:1 48e49
Linoleic Cis-9, cis-12-octadecenoic C18H32O2 18:2 18e19 Moisture 8.05
Arachidic Eicosanoic C20H40O2 20:0 4e5 Volatile organic matter 41.85
Behenic Docosanoic C22H44O2 22:0 4.5e5.5 Ash 3.21
Lignoceric Tetracosanoic C24H48O2 24:0 2.5-3.5 Fixed carbon 46.89
 B. Karmakar et al. / Journal of Cleaner Production 255 (2020) 120313 5

Fig. 1. Thermo-gravimetric analysis (TGA) and derivative thermo-gravimetry (DTG) of raw Delonix regia pods.

Fig. 2. SEM image of (a) carbonized Delonix regia (b) steam activated Delonix regia (c) H2SO4 impregnated Delonix regia (d) KOH impregnated Delonix regia.
6 B. Karmakar et al. / Journal of Cleaner Production 255 (2020) 120313
catalyst (Fig. S1a) a high concentration of S and O is seen, while for
the KOH-doped catalyst (Fig. S1b), a very high amount of K is seen,
which confirms effective doping.
FT-IR and XRD analysis confirm presence of various functional
groups. Spectral data from the FT-IR analyses of the samples are
shown in Fig. S2 where the presence and modification of charac-
teristic peaks at specific wavenumbers confirm the success of the
physical activation as well as the changes caused in the surface
structure of the catalyst support due to wet impregnation processes
for both H2SO4 and KOH. For each sample, various characteristics
peaks were obtained. For steam activated carbon: 3512 cm1 de-
notes a OeH phenol group, 3438 cm1 denotes a secondary NeH
amine stretch (Dhawane et al., 2017), 3394 cm1 denotes OeH
carboxylic acid group, 1610 cm1 and 1646 cm1 denote C]C
alkene stretches, 1590 cm1 denotes a secondary NeH amide bend
(Dhawane et al., 2015) and 930 cm1 denotes CeH alkene stretches
(Dhawane et al., 2016b). For sulfonated carbon: 3609 cm1 denotes
an OeH alcohol group (free), 3482 cm1 and 3421 cm1 denote
NeH primary and secondary amine stretches correspondingly
(Roldan et al., 2012), 3226 cm1 is formed due to an OeH alcohol
group (H-bonded), 1636 cm1 and 1616 cm1 show C]C weak
alkene stretches, 1368 cm1 denotes a S]O sulfone group while
1194 cm1 confirms H2SO4 adsorption (Bora et al., 2018) and
1050 cm1 denotes a sulfoxide group. For KOH doped catalyst,
similar peaks are also noted, with minor changes in the peak po-
sitions. The peaks noted for base catalyst were at: 3618 cm1,
3510 cm1, 3226 cm1, 1639 cm1, 1620 cm1, 1501 cm1 and
930 cm1. The results obtained from the XRD analysis help us
comprehend the presence and structure of the polycyclic rings of
aromatic carbon. Their presence results in the effective surface
doping of H2SO4 or KOH on the activated carbon support (Budarin
et al., 2006; Lokman et al., 2016; Yu et al., 2010; Zong et al., 2007).
The peaks observed within the 2q range of 10
e30
can be seen in
Fig. S3, with peaks at 24
, 40.38
confirm a carbonaceous support.
Also shown in Fig. S3 is the diffraction pattern for sulfonated car-
bon. The intensities of the peaks are seen to increase in the 2q range
20
e30
and 40
e50
which corresponds to effective doping of
H2SO4 (Konwar et al., 2014). When KOH is impregnated on the
activated char, its dispersion on the surface of the char as seen in
Fig. S3 can be ascertained by the 2q peaks seen at 12.28
, 23.74
and
28.26
. Among these, a peak noted at a 2q value of 12.28
confirms
that the support surface has been doped by KOH. All the values for
the diffraction data can be related to their characteristic structures
by referring to the standard JCPDS library (Dhawane et al., 2015).
Thus it can be confirmed that the process of steam activation and
doping of H2SO4 and KOH on to the inert carbonaceous support was
successful, with resistance to leaching resulting in high reusability
shown in Section 4.
3.3. ANOVA of the two-step production process
Optimization of the biodiesel production was done with the use
of L16 Taguchi matrices, one for the acid esterification process that
is focussed on converting FFA to FAME, while the other matrix is for
biodiesel production from the esterified oil using 2-propanol. The
response obtained for each combination of parametric conditions
can be useful in the determination of the process’s optimum con-
ditions. For the acid esterification process the drop in acid value
represents the formation of FFA into their corresponding methyl
esters, as seen in Table 3 and the base transesterification process is
concerned with the conversion of the triglycerides into FAPE as
shown in Table 4 (Dhawane et al., 2018).
The ANOVA technique being vigorous, it can be used to develop
a mathematical model equation and to examine the model’s
acceptability for process optimization. Statistical analysis of both
the esterification and transesterification techniques can be per-
formed by ANOVA studies of the response in each case. For each
model thus developed, values for the sum of squares, the F-value
(Fisher’s exact test) and the p-value (probability) describe its sig-
nificance in process optimization and how each process variable
impacts the response. ANOVA results for both processes have been
reported in Table S3 and S5. From the ANOVA results of FFA ester-
ification, it is seen that the F-value is 13.24 with a p-value of 0.028,
indicating that the model terms are significant. Similarly from the
ANOVA results of glyceride transesterification, it is seen that the F-
value is 38.65 with a p-value of 0.0059. The sum of squares (SS)
values for both the processes are also listed, and for each process,
the SS values of each process parameter can be computed into its
corresponding contribution factor for the reaction using Eq. (4). The
contribution factors for every significant process parameter both
the esterification and transesterification processes are represented
in Table 5. These show that for the esterification process, agitation
speed had the highest controlling effect on the reaction, while for
the transesterification process, it was reaction time.
For the estimation of fit characteristics of the model, the pre-
dicted R2 value should be close to the adjusted R2 value, with a
maximum difference of 0.2. When the difference is higher than 0.2,
it is most likely that this is caused by a large block effect or an error
with the data or more likely, the model chosen. Also, the adequate
precision value which tests the ratio of signal to noise (SNR) should
be high enough, the minimum desired value being 4 (Dhawane
et al., 2016b; Kilic et al., 2013). For both the processes, the values
are in reasonable agreement for the model to be acceptable, as is
represented in Tables S4 and S6.
3.4. Regression model equation and experimental validation
The regression model equation developed from the ANOVA
studies is useful in interpreting the significance of individual pa-
rameters upon the process response, and the coefficients associated
with each of the different levels considered for every factor in the
equation are useful in understanding the relative impact on the
overall process. For both the acid esterification and the base
transesterification processes, two separate model equations were
developed that depicted the response in terms of FFA conversion
and biodiesel yield, as shown in Eqs. (5) and (6):
FFA Conversion (%) ¼ 71.14 þ 1.36  A[1] þ 7.49  A[2] - 4.96  A
[3] þ 4.78  C[1] þ 6.98  C[2] e 6.81  C[3] þ 0.7488  D
[1] þ 4.14  D[2] þ 5.22  D[3] e 8.02  E[1] e 5.67  E
[2] þ 9.03  E[3] (5)
Biodiesel yield (%) ¼ 97.34e0.5094  A[1] e 0.0044  A
[2] þ 0.7456  A[3] e 1.82  B[1] þ 0.6681  B[2] þ 0.4631  B[3] e
0.8219  C[1] þ 0.6281  C[2] þ 0.4431  C[3] þ 0.0706  E
[1] þ 0.7706  E[2] e 0.8619  E[3] (6)
For Eqs. (5) and (6) (wherever applicable), A represents reaction
temperature, B represents reaction time (duration), C is the catalyst
concentration, D refers to the alcohol:oil ratio (methanol for
esterification and 2-propanol for transesterification) and E refers to
the agitation speed. 1, 2 and 3 refer to the levels of each process
parameter that affect the reaction in each case. According to Figs. 3
and 4, the one factor model graphs show the optimum levels for
each significant process variable (a to d) that is included in the
model equations for FFA conversion and biodiesel yield. Thus, the
figures clearly show that the coded equations are efficient in precise
prediction of the required response (Dhawane et al., 2015). From
the ANOVA analysis and the factors coded in the model equation,
the set of reaction parameters at their optimum levels can be
 B. Karmakar et al. / Journal of Cleaner Production 255 (2020) 120313 7

Table 3
L16 experimental matrix for esterification depicting FFA conversion.

Run No. Temperature (
C) Time (min) Catalyst (w/w %) Methanol: oil molar ratio Agitation Speed (rpm) FFA conversion (%)

1 60 180 3 6:1 900 83.33

2 50 180 4.5 9:1 600 68.33
3 70 45 6 9:1 900 72.67
4 60 135 1.5 9:1 1050 81.17
5 70 135 3 15:1 600 57.5
6 40 90 3 9:1 750 78.96
7 40 135 4.5 12:1 900 81.36
8 70 90 4.5 6:1 1050 66.84
9 60 90 6 12:1 600 59.44
10 60 45 4.5 15:1 750 40.77
11 50 45 3 12:1 1050 92.67
12 40 45 1.5 6:1 600 67.19
13 40 180 6 15:1 1050 62.5
14 50 135 6 6:1 750 70.19
15 70 180 1.5 12:1 750 71.97
16 50 90 1.5 15:1 900 83.33

Table 4
L16 experimental matrix for transesterification depicting biodiesel yield.

Run No. Temperature (
C) Time (min) Catalyst (w/w %) Methanol: oil molar ratio Agitation Speed (rpm) Biodiesel yield (%)

1 50 150 6 8:1 600 98.53

2 40 150 8 12:1 900 97.12
3 60 60 6 12:1 700 97.31
4 40 60 2 6:1 600 94.41
5 50 90 2 12:1 800 96.15
6 70 150 2 10:1 700 97.76
7 50 120 8 6:1 700 98.47
8 60 150 4 6:1 800 98.69
9 40 120 6 10:1 800 96.89
10 60 120 2 8:1 900 97.74
11 50 60 4 10:1 900 96.18
12 60 90 8 10:1 600 98.59
13 40 90 4 8:1 700 98.89
14 70 60 8 8:1 800 94.17
15 70 90 6 6:1 900 98.39
16 70 120 4 12:1 600 98.1

Table 5
Parametric contribution percentage and optimum values for FFA conversion%.

Parameter (unit) FFA Conversion (Acid esterification) Biodiesel production (Base transesterification)

Contribution Factor (%) Optimum value Contribution Factor (%) Optimum value

Agitation speed (rpm) 34.03 900 16.81 700

Alcohol: oil ratio 25.08 (with methanol) 12:1 Insignificant (with 2-propanol) 6:1
Catalyst Concentration% (w/w) 24.24 3 16.62 4
Reaction temperature (
C) 16.65 50 10.89 60
Reaction time (h) Insignificant 45 55.67 90

Table 6
Analysis of karanja oil and biodiesel obtained.

Parameter (unit) Karanja oil Biodiesel obtained Testing Procedure

Relative density (at 25
C) 0.89 0.754 ASTM D4253

Acid Value (mg KOH/g) 16.83 0.024 ASTM D974
Free Fatty Acid (%) 8.46 0.012 -
Kinematic viscosity (mm2/s) 24.71 2.3 ASTM D445
Water content (%) 0.21 0.02 ASTM D3172
Calorific value (MJ/kg) 36.5 39.8 ASTM D240
Flash Point (
C) - 179 ASTM 6450
Fire Point (
C) - 190 ASTM 6450
Aniline Point (
C) - 49 ASTM D611
Cetane Number - 56.1 ASTM D613
Diesel Index - 64.03 -
8 B. Karmakar et al. / Journal of Cleaner Production 255 (2020) 120313

Fig. 3. Impact of reaction parameter on FFA conversion: (a) Reaction temperature (b) Catalyst concentration (c) Methanol:oil ratio and (d) Agitation speed.

obtained. However, for establishment of the accuracy of the
mathematical prediction, the reaction conditions need to be
experimentally validated. For validation, experimental runs are
carried out and the response tallied against the predicted results.
The predicted versus actual values can then be plotted as shown in
Figs. S4 and S5, which show good correlation with negligible dif-
ferences, confirming the model’s accuracy in response prediction,
for both FFA conversion and biodiesel yield.
transesterification. Both esterification and transesterification pro-
cesses depend on the variation of process parameters that have
their individual as well as combined effects. This study was directed
at optimization of reaction parameters for both processes, listed as:
agitation speed, reaction temperature, catalyst load in the reaction
mixture, molar ratio of alcohol to oil and reaction duration. Optimal
levels corresponding to their values for both FFA conversion and
biodiesel yield are summarily reported in Table 5.

3.5. Parametric analysis of two-step conversion 3.5.1. Impact of reaction temperature

Separate experiments were conducted using 2-propanol for acid
pre-treatment. The 2-propanol greatly improves acid trans-
esterification but doesn’t react with the FFAs at all, hence the
product degrades within 48e72 h. Hence, the alcohol added is
methanol for acid esterification and 2-propanol for base
A temperature at which the reaction is allowed to take place is a
key factor in determining the reaction efficiency since low tem-
peratures provide insufficient energy towards product formation,
while high temperatures lead to product degradation with reactant
losses. When methanol is used for esterification, temperatures
higher than the boiling point of ethanol (64.7
C) are usually
 B. Karmakar et al. / Journal of Cleaner Production 255 (2020) 120313 9

Fig. 4. Impact of reaction parameter on FFA conversion: (a) Reaction temperature (b) Reaction time (c) Catalyst concentration and (d) Agitation speed.

unfavourable since most of the methanol will exist in vapour form
and therefore will be unable to react with the oil. The same goes for
base transesterification with 2-propanol, however, in this case
increased miscibility between the reactants means that the
required temperature for maximum product can be expectedly
moderate enough. For the esterification process, the reaction
temperature was changed through 4 levels between 40
and 70
C.
According to the conclusions drawn from Fig. 3a, the yield
improved up to 50
C, declining rapidly on further increase. As
mentioned earlier, rapid evaporation of methanol is common at
higher temperatures and methanol vapours cannot react with the
oil. Comparable observations were noted from various other ex-
periments (Dhawane et al., 2017, 2018; Halder et al., 2015;
Karmakar et al., 2018; Neeharika et al., 2017). Similarly, for base
transesterification, the reaction temperatures were also varied at 4
levels between 40
C and 70
C, and the graph presented in Fig. 4a
also represents a similar finding, when 2-propanol was used as the
reacting alcohol. The yield improved till 60
C followed by a mild
decline on further increase to 70
C. This can be due to the increase
in backward reaction favored by increased vaporization of the
alcohol.
3.5.2. Impact of reaction time
For a reaction to be complete, the reactants should have enough
residence time so that the molecules can interact as long as
required for the desired products to be formed. With a high reac-
tion rate, the duration needed is low (Bokhari et al., 2016). When
the reactants are in the same phase but are immiscible, reaction
duration can expectedly be higher (as in acid esterification), with
miscibility leading to faster reaction rates (as in base trans-
esterification) For FFA conversion, the reaction duration was varied
at 4 levels between 45 min and 180 min, and 45 min was sufficient,
10 B. Karmakar et al. / Journal of Cleaner Production 255 (2020) 120313
indicating a rapid reaction. Analogous results were obtained by
Medina-Valtierra et al., with catalyst developed from pyrolyzed
rubber tyre waste (Medina-Valtierra et al., 2017) and by Dhawane
et al., who converted rubber seed oil in their experiments using
Fe(II) as well as KOH doped carbonaceous catalyst in separate
studies (Dhawane et al., 2016a, 2016b).
For the base-catalysed transesterification using 2-propanol, the
reaction duration was varied at 4 levels between 60 min and 150 min
at 30 min intervals. Fig. 4b depicts the results, where it is discernible
that the yield of propyl esters was seen to increase considerably till
90 min, with further increase having an insignificant effect. This is
due to the high reaction rate since 2-propanol and oil are miscible. In
other works with lower alcohols, various researchers reported re-
sults that were similar, showing the impact of reaction duration on
the optimization of biodiesel yield using both acid and base catalysed
approaches (Bokhari and Chuah, 2016; Bora et al., 2018; Dhawane
et al., 2015; Goyal et al., 2012; Halder et al., 2015).
3.5.3. Impact of alcohol to oil ratio
In a typical transesterification and esterification, 3 mol of
alcohol convert a triglyceride into 3 fatty acid esters (biodiesel),
while 1 mol of alcohol is required to convert an FFA mole in the oil
to its ester (Bokhari and Chuah, 2016). In this study, methanol was
chosen for esterification since secondary alcohols with higher car-
bon chain length do not react with FFAs due to low polarity of the
alkyl group and steric hindrance. While the alcohol provided
should be in excess of the stoichiometrically required amount, a
large excess leads to dilution, inhibiting reaction progress
(Dhawane et al., 2017). In the esterification step, it was noted from
Fig. 3c that highest FFA conversion occurred at ratio of 12:1. Thus,
methanol is required in a large excess than is dictated by stoi-
chiometric ratios. Since the esterification reaction is easily revers-
ible, this excess helps in keeping the reaction equilibrium towards
product formation. From Table 5 it can be seen that this parameter
has a significant contribution of 24.24% in the FFA conversion
process. Studies reported by many others (Berrios et al., 2007;
Neeharika et al., 2017; Ramachandran et al., 2011; Wan Omar et al.,
2009) are in agreement with our reported conclusions.
For the base catalysed transesterification using 2-propanol, the
resistance in diffusion is negligible. Therefore the lowest amount of
2-propanol is sufficient in providing optimum biodiesel yield with
the optimization approach (L16 Taguchi OA) showing the insigni-
ficance of this process parameter on the biodiesel yield. Hence, the
lowest level of this parameter, i.e., a 6:1 M ratio is chosen, keeping
cost-effectiveness in mind.
3.5.4. Impact of catalyst concentration
Catalyst concentration is seen to be influential in the FFA
reduction, since a significant catalyst quantity is required to facili-
tate esterification as seen from Fig. 3b. Since the catalyst is het-
erogeneous, this would mean that 3% w/w is chosen (due to being
economical) for further experiments. From Table 5, it is seen that
catalyst concentration has a significant contribution in FFA con-
version, by a percentage of 24.24%. Studies by Bora et al. using
sulfonated MFL char on MFL oil into biodiesel resulted in similar
conclusions (Bora et al., 2018). In some other studies using H2SO4 in
a direct-homogeneous system (Agra et al., 1996; Banani et al., 2015;
Bokhari and Chuah, 2016; Goyal et al., 2012) it was shown that
increase in acid catalyst concentration had trivial impact on the FFA
conversion or biodiesel yield.
During the second stage using base catalyst (KOH impregnated
char), the catalyst concentration at 4% w/w was seen from Fig. 4c to
have the highest biodiesel yield. This can also be explained due to
the leaching of the KOH into the system from the carbon support
and thereby causing minor amounts of saponification with the
residual FFA in the oil, which can therefore attribute to the drop in
biodiesel yield. Studies on Hevea brasiliensis oil using flamboyant
pod support for KOH impregnated base catalyst and Fe(II) doped
metal catalyst have been reported by Dhawane et al. with similar
conclusions (Dhawane et al., 2016a,b, 2017).
3.5.5. Impact of agitation speed
Even when the oil and alcohol are mixed and heated to a suitable
temperature, the FFA esterification or triglyceride transesterification
do not occur unless external agitation is provided to the reactants.
Most reported literature works reported before have considered a set
agitation speed for carrying out their experimental works; however,
it should be considered for optimization. From the acid esterification
data depicted in Table 3 and Fig. 3d when optimization of FFA con-
version is carried within a range of 600 rpme1050 rpm, it is seen
that optimal ester yield was at 900 rpm, while additional escalation
caused a fall in ester conversion. The reported results are congruent
to our other works (Karmakar et al., 2018), to the observed trend
reported by Aldo et al. and Ramachandran et al. (Aldo et al., 2010;
Ramachandran et al., 2011).
Similarly, for base transesterification as seen in Fig. 4d,
when the variation of the mixing intensity was done within
the range of 600 rpme900 rpm, an increase in biodiesel yield
was noted from 600 to 700 rpm, after which the yield dropped
abruptly at 800 rpm, with better yields at 900 rpm. Hence the
agitation speed of 700 rpm is considered optimal. For both
acid esterification and base transesterification reactions, if the
mixing intensity is extreme, the reactants do not get sufficient
contact time for the reaction to proceed. The rapid collisions
between reactant molecules that results from extreme agita-
tion not only results in damage of the structural integrity of
the catalyst, but also inefficient product formation. Similar
results were observed by Dhawane et al. in their works
(Dhawane et al., 2016b, 2017).
3.6. Fuel characterization
The acid esterified oil must have a low FFA content (as signified
by its low AV) for the base transesterification process. Also,
physico-chemical properties of the biodiesel must be tested for
suitability as fuel. Characterization was done through standard-
ized ASTM tests and found to adhere to required specifications.
These included tests for residual AV and FFA% content for both the
esterified oil and the biodiesel, while other tests such as flash
point, aniline point, cetane number, diesel index (DI), fire point,
kinematic viscosity (KV), molecular weight, relative density,
calorific value and water content. All of these were tested and
reported summarily in Table 6. Fire point and flash point tests
showed high thermal stability of the fuel, since flash point is
179
C. Residual AV and FFA are noted to be 0.64 and 0.32
respectively, indicating the fuel’s non-corrosive nature. KV of the
fuel is 2.3 mm2/s, indicating good fuel fluidity resulting in
improved spray characteristics (Ahmad et al., 2019). Calorific
value was also tested and the value indicates that high amount of
heat energy from the fuel can be obtained. The high aniline point
noted can be attested to a high paraffinic content. High amounts of
paraffin are desired and sometimes even added to enhance the
combustion of the fuel. This also corresponds to the diesel index
(DI) of the fuel being high, and the fuel can be expected to show
low ignition delay resulting from a higher cetane number when
compared to petro-diesel (values within 45e48). Every value
tested for each property was found to be adhering to the ASTM
limits set for commercial biodiesel, with some values that were
better than known for petro-diesel. These values for the fuel
alongside the values for those of the raw karanja oil are shown in
 B. Karmakar et al. / Journal of Cleaner Production 255 (2020) 120313 11

Table 6. Hence it is clear that the fuel obtained through the rec-
ommended two-step production process when performed under
optimal conditions can be used in diesel engines (when blended
suitably) since it is better than commercially recommended
biodiesel.
4. Raw material drying cost (DC) ¼ Time in hours  units
consumed  cost per unit ¼ 12  2  $0.065 ¼ $1.56
5. Carbonization costs (CC) ¼ IEC þ HC ¼ $ (0.044 þ 0.58) ¼ $0.624
where IEC is the inert environment creation cost.
IEC ¼ N2 flow ¼ $0.044

4. Catalyst reusability HC ¼ Time in hours  units consumed  cost per

unit ¼ 1.5  6  $0.065 ¼ $0.58
After the first use, the heterogeneous acidic and basic catalyst
were collected by filtration and washed with acetone for the
6. Steam activation cost (AC) ¼ SC þ HC ¼ $
removal of oil and impurities, then dried in a hot air oven. Cata-
(0.065 þ 0.38) ¼ $0.445, where SC refers to steam preparation
lysts were reused in different concentrations (other parameters at
cost and HC is the heating cost.
optimal levels) for evaluation of the reusability and to check the
efficiency of functional group retention by the carbon support, as
SC ¼ Time in hours  units consumed  cost per
in Table S7. When the drop in FFA conversion or biodiesel yield
unit ¼ 1  1  $0.065 ¼ $0.065
was significant enough, the carbon support was again impreg-
nated with H2SO4 or KOH as described in Section 2.2. From
HC ¼ Time in hours  units consumed  cost per
analysis of the products of the esterification and trans-
unit ¼ 1.5  4  $0.065 ¼ $0.38
esterification processes, it was seen that catalytic activity of the
sulfonated carbon decreased significantly after 3 reuses while the
KOH doped carbon retained its efficiency till 7 reuses. This is due  Therefore raw material creation cost:
to functional group leaching (both H2SO4 and KOH) during the
reaction as well as from the structural damage of the inert sup- CC þ DC þ WC þ SRC þ RMC þ AC ¼ $0.624 þ $1.56 þ $0 þ $0
port due to agitation (Dhawane et al., 2016a). The prepared cat- þ$0 þ $0.445 ¼ $2.629
alysts thus are able to remain efficient till quite a number of
reuses, while the structural integrity of the carbon support is not
7. Cost of impregnation (IC) ¼ AGC þ CCH
compromised even after many reuses. When combined with the
¼ $(8.45 þ 103.536) ¼ $111.986, where AGC refers to the cost of
ease of recovery and reuse (filtration followed by washing), the
agitation, while CCH is the cost for chemicals required for
catalysts show tremendous potential in large scale applications
impregnation.
where bulk quantities of catalyst can be easily prepared with the
right equipment as well as reuse for cost effectiveness is also a
AGC ¼ Time in hours  units consumed  cost per unit ¼
major advantage.
(10  1  $0.065) þ (24  5  $0.065) ¼ $8.45

5. Cost analysis for catalyst preparation CCH ¼ [amount of H2SO4 needed (in litre)  cost per
litre] þ [amount of KOH needed (in kg)  cost per kg] ¼
For the presented work, catalyst preparation cost assessment is (4  $10.47) þ (5.6  $11.01) ¼ $103.536
useful for understanding if the process is appropriate for
commercialization. Among all factors, most of the cost is due to
 Net cost involved ¼ CC þ DC þ WC þ SRC þ
factors like source of raw material, preparation technique,
RMC þ IC þ AC ¼ $2.629 þ $111.986 ¼ $114.615
required treatment process and especially reusability. In the
 Total cost ¼ Net cost þ Overhead charges (10% of net
preparation of 1 kg each of sulfonated and KOH-doped catalyst,
cost) ¼ $114.615 þ $11.462 ¼ $126.077
the following were our observations, which have been calculated
in USD ($).
From the cost analysis shown above, two things are quite clear:
1. Raw material cost (RMC) ¼ $0 (waste material, locally available).
1. The cost of preparation of raw material is quite negligible in
For commercial production, 10% overhead cost allotted collec-
bulk.
tion labour charge.
2. More than 90% of the catalyst preparation cost comes from the
2. Size reduction cost (SRC) ¼ $0 for batch studies since reduction
cost of chemicals required for impregnation.
was manual. For commercial production, 10% overhead cost
allotted (machine grinding).
Under optimum conditions and maximum reuse, the lowest
3. Cost for raw material washing ¼ HC þ WC ¼ $0.064 where WC is
yield of 95.61% is reasonably significant. From the reusability
the water cost since distilled water acquired from distilled water
studies, it was also seen that while the sulfonated carbon can be
setup available in laboratory is used and HC is the heating cost
reused 3 times, the KOH doped carbon is more stable in retaining
involved in obtainment of the distilled water.
the functional groups in its matrix and can be reused very effi-
ciently till 7 times. Hence, using 2 kg of sulfonated carbon and
HC ¼ (unit cost for 1 L water  units 1.33 kg of KOH-doped carbon catalysts, an approximate amount of
consumed) ¼ $0.065  1 ¼ $0.065 267 kg biodiesel can be developed, with catalyst cost accounting for
an amount of $211 in total, or only $0.79 per kg. The sole factor for
WC ¼ $0 (water cost already included in HC) this drastic cost reduction is the reusability. According to recent
sources, market price of commercial grade AC is over $14.5, which
12 B. Karmakar et al. / Journal of Cleaner Production 255 (2020) 120313
is very high compared to our $1.38 spent in AC preparation. Hence it
is apparent that the process has a lucrative scope for commercial-
ization owing to the low costs incurred in carbon support prepa-
ration as well as the relatively simple catalyst preparation process.
The recovery and reuse of the catalysts is also simple enough on a
large scale with the right equipment, and since the carbon support
prepared is structurally very capable of retaining functional groups
as well as not damaged during the reaction and washing, Delonix
regia based catalysts are definitely a rewarding approach towards
large scale catalysed biodiesel production.
6. Conclusions
A new technique was adopted for production of a low-corrosion
biodiesel using a two-step catalytic conversion using steam acti-
vated Delonix regia as inert support for both acid (H2SO4 doped) and
base catalysts (KOH doped). Raw material used as feedstock for the
process is karanja oil. Using L16 Taguchi DOE, both esterification
and transesterification processes are optimized. For both processes,
the following parameters were considered: catalyst load, reaction
duration, reaction temperature, molar ratio of oil to alcohol and
agitation speed. Raw pods were analysed using TGA for determi-
nation of fixed carbon and carbonization temperature. Activated
char and developed catalysts were characterized using SEM, EDAX,
FT-IR, XRD and BET. The produced biodiesel was characterized by
standard ASTM tests for physico-chemical suitability of the prod-
uct. The developed catalysts were also tested for reusability, and
base catalyst showed more stability in functional group retention
than the acid catalyst. Finally an analysis of cost for preparation of
the catalyst was calculated. Maximum FFA conversion using
methanol was 99.86%; maximum biodiesel production using 2-
propanol was 99.39%. Biodiesel production reaches a maximum
of 99.39% at 60
C for 90 min with 4% w/w catalyst under 700 rpm
using 6:1 2-propanol: oil ratio. Catalyst reusability experiments
showed good FFA conversion till 3 re-uses and high biodiesel yield
till 7 re-uses. Cost analysis showed that catalyst support when
indigenously prepared, is much more economical compared to
activated carbon that is available commercially.
Declaration of competing interest
The authors declare that they have no known competing
financial interests or personal relationships that could have
appeared to influence that work reported in paper.
CRediT authorship contribution statement
Bisheswar Karmakar: Conceptualization, Methodology, Inves-
tigation, Software, Validation. Sucharita Samanta: Formal analysis,
Data curation, Writing - original draft. Gopinath Halder: Supervi-
sion, Project administration, Writing - review & editing.
Acknowledgements
We express our sincere gratitude to the Ministry of Science and
Technology, Govt. of India for their financial aid through research
project no. EEQ/2016/000243.
Appendix A. Supplementary data
Supplementary data to this article can be found online at
https://doi.org/10.1016/j.jclepro.2020.120313.
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