Renewable and Sustainable Energy Reviews 116 (2019) 109394

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Renewable and Sustainable Energy Reviews

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Biodiesel production from waste cotton-seed cooking oil using microwave- T

assisted transesterification: Optimization and kinetic modeling
Anvita Sharmaa,c, Pravin Kodgirea,c,∗, Surendra Singh Kachhwahab,c
a
Chemical Engineering Department, Pandit Deendayal Petroleum University, Gandhinagar, 382007, Gujarat, India
b
Mechanical Engineering Department, Pandit Deendayal Petroleum University, Gandhinagar, 382007, Gujarat, India
c
Centre for Biofuels and Bioenergy Studies, Pandit Deendayal Petroleum University, Gandhinagar, 382007, Gujarat, India

A R T I C LE I N FO A B S T R A C T

Keywords: The current research focuses on process optimization and kinetic study of microwave-assisted transesterification
Waste cotton-seed cooking oil process using KOH and CaO catalyst from waste cotton-seed cooking oil (WCCO). In order to enhance the
Microwave irradiation biodiesel yield, process parameters: methanol to oil ratio (A), catalyst loading (B) and reaction time (C) were
Homogeneous KOH catalyst optimized by applying response surface methodology based on full factorial design method. It was found that for
CaO catalyst
KOH catalyzed condition, the optimum values for A, B and C are 7:1, 0.65 (w/w) % and 9.6 min, respectively and
Full factorial design of experiment
Scale-up studies
the model predicted yield is 96.44%. For CaO catalyzed condition, the optimum values for A, B and C are 9.6:1,
1.33 (w/w) % and 9.7 min, respectively and the predicted yield is 89.94%. Experiments were performed using
the optimized parameters and the mean biodiesel yield determined for KOH and CaO catalyzed conditions are
96.55 ± 0.23% and 90.41 ± 0.02%, respectively which shows good agreement with model predictions.
Analysis of perturbation plots showed that catalyst loading is the most sensitive variable. Considering pseudo-
first-order kinetic, the activation energies were obtained and found to be 13.05 kJ mol-1 and 28.93 kJ mol-1
respectively for KOH and CaO catalyzed conditions. The activation energy observed for microwave-assisted
method are significantly lower compared to that of conventional method. The scale-up study (with 10 fold batch-
size) and energy analysis have been done for KOH and CaO catalyzed conditions whereas reusability was per-
formed with CaO catalyst. It was observed that up to four cycles the biodiesel yield achieved was more than 90%.
In microwave-assisted process, efficency factor found to be higher as compared to conventional method. The
produced biodiesel properties fulfill fuel specifications designated as per ASTM D6751 standard. The outcome of
microwave-assisted transesterification study enhances biodiesel yield and significantly decreases the reaction
time, thus making it energy-efficient technique.

1. Introduction renewable fuels.

World energy requirements are primarily satisfied by use of fossil
fuels. It is well-known that burning of coal and crude based fuel leads to
environmental concerns such as air pollution, greenhouse effect, waste
disposal and climate change, etc. [1]. It is one of the primary challenges
that need full engagement from all the concerned stakeholders [2]. The
carbon footprint increased, especially by automobile and allied sectors,
plays a vital role on issues of environmental health [3]. Hence, attempts
are made to bring diversity of renewable fuels used in vehicles. This
approach is one of the efficient solutions to counter environmental
problems caused by combustion of non-renewable fuels [4,5]. Biodiesel
plays a significant role in satisfying the demand for sustainable alter-
native fuel, which will help in reducing carbon footprint [6]. Biodiesel
is biodegradable and environment friendly option as compared to non-
According to recently published statistical data by Petroleum
Planning and Analysis Cell of Oil Ministry (Government of India),
consumption pattern of high-speed diesel demand has seen a growth of
6.6% till March 2018 [7]. Due to the high demand of petroleum pro-
ducts, there has been a hike in the price of petroleum products both
nationally and internationally [8]. Thus, these reasons have strength-
ened the need to introduce alternative renewable fuel which can be
produced locally, and reduce the dependency on fossil fuel [9,10]. As
per the national policy on biofuels (Biofuels-2018), a target of 5%
biodiesel blending is proposed by 2030. Till 2018, India has achieved
only 0.12% blending [11].
Biodiesel being a renewable fuel is produced from various feedstock
[9,12–20]. A major challenge related to sustainable biodiesel produc-
tion is cheaper and readily available raw materials, which delays the

∗
Corresponding author. Chemical Engineering Department, Pandit Deendayal Petroleum University, Gandhinagar, 382007, Gujarat, India.,
E-mail address: pravin.kodgire@sot.pdpu.ac.in (P. Kodgire).

https://doi.org/10.1016/j.rser.2019.109394
Received 20 November 2018; Received in revised form 14 August 2019; Accepted 12 September 2019
1364-0321/ © 2019 Elsevier Ltd. All rights reserved.
A. Sharma, et al. Renewable and Sustainable Energy Reviews 116 (2019) 109394

Table 1
Summary of literature studied for microwave-assisted biodiesel production using WCO and the respective key findings.
Author (Year) [Ref.No.] Feedstock Reactor Details Process Parameters Type of DOE Key Findings

Saifuddin and Chua (2004) [66] Used frying oil Microwave oven (model RM 800, Batch: 250 g – 87% conversion
Plazmatronika, Wroclaw, Poland) KOH: 1 wt % Time: 4 min
Power: 750 W NaOH: 0.5 wt %
Time: 3–5 min
Lertsathapornsuk et al. (2008) [67] Waste frying Modified domestic microwave NaOH: 3 wt % – 97% Yield
palm oil Power: 80 0 W E:O-12:1
Continuous mode Time: 30 s
Yaakob et al. (2009) [68] Waste frying MW650 (Lab microwave) M:O- 12:1 – 88.63% yield
palm oil Power: 25% of 1250 W NaOH%- 0.5–1.5 wt % Temp: 65 °C
Temp: 60–70 °C Time: 7 min
Time 6–8 min NaOH wt %: 1%
Rahmanlar et al. (2011) [69] Waste frying Milestone, Microsynth NaOH: 0.5–1.5 wt % – 97.20% yield
oil Temp: 64 °C NaOH-1 wt %
M:O- 6:1 to 18:1 M:O- 9:1
Time: 1–15 min Time: 3 min
Patil et al.(2012) [70] Waste cooking Modified Domestic Microwave M:O- 6:1 to 15:1 – 92% Yield- KOH
oil Power: 800 W Catalyst: 1–2 wt % 96% Yield - BaO
Time: 6 min 10% less energy
consumption
M:O- 9:1
KOH, BaO %- 2 wt %
M:O- 12:1
Chen et al. (2012) [71] Waste cooking Microwave synthesis reactor Power: 200–750 W – NaOH and CH3ONa: 0.75 wt
oil (NNS235, Panasonic Ltd) Time: 3 min %
Stirring: 600 rpm Time: 3 min
Time: 1–6 min M:O- 6:1
M: O - 3–15:1 Power- 750 W
Azcan and Yilmaz (2013) [72] Waste frying Start S model microwave NaOCH3- 0.5 – 1.5 wt % – 90.04–98.85% yield
oil Time: 3–9 min
Temp: 55–65 °C
Mazubert et al. (2014) [73] Waste cooking CEM Discover SP M: O- 4–6:1 – Esters: 91.3 ± 1%
oil Power: 300 W Stirring: 300 rpm Activation energy: 37.1 kJ/
Batch: 80 mL mol
Temp: 30–60 °C
Time: 20–45 s
Priambodo et al. (2015) [74] Waste cooking Panasonic NN-SF550 Time: 40–180 s – 93% yield
oil Power: 1000 W Temp: 80 °C M:O- 6:1
M: O- 4–10:1 SrO:1.85 wt %
SrO: 1.4–3.25 wt % Time: 3 min
In Kwon Hong et al. (2016) [75] Waste cooking Mars- 2 M:O- 0.4 – 1.2:1 – M:O- 8:1
oil Power: 300–700 W Time: 6 min
Time: 2–10 min Power: 500 W
Stirring: 1000 rpm KOH:1 wt %
Batch: 50 g Power: 600 W
KOH:1.2 wt %
96.5% yield
Tangy et al. (2016) [76] Waste cooking Modified Domestic Microwave Batch: 15 g – 99.4% yield
oil SrO @ SiO2: 0.5 g
Time: 10 s
Temp. 333 K
Tangy et al. (2017) [77] Waste cooking Flow SYNTH microwave system Batch: 190 mL – 99.2% yield
oil Power: 1000 W O:M − 1:6 to 1:12 15 g of 41 wt % SrO/SiO2
SrO: 5–8.75 g catalyst
Feed rate: 0.06–3400 mL/ Time: 8.2 min
min Feed rate: 820 mL
Temp: 200 °C
Pressure: 30 bar
Panadare and Rathod (2017) [78] Waste cooking ANTON-PAAR Multiwave PRO Batch: 20 mL – 94% yield
oil Power: 70 W Dimethyl carbonate: WCO – Time: 240 min
2–12:1 First order kinetics
Enzyme: 5–15 wt % Activation energy:
Temp: 50–70 °C 18.96 kJ/mol
Thirugnanasambandham et al. Waste cooking Modified Domestic Microwave Batch:30 g Box-Behnken model Optimum power: 325 W
(2017) [79] oil Time: 200 s
Temp:70 °C
KOH wt %-1 g/g
97% yield
Xiang, Xiang and Wang (2017) [80] Waste cooking Modified Domestic Microwave Batch: 10 mL Central composite 94.91% yield
oil M:O- 3 – 11: 1 design M:O- 9.67:1
Flyash wt %- 2–10% Flyash wt %: 3.99%
Temp: 50–90 °C Temp: 66.20 °C
Time: 6 min
Gupta and Rathod (2018) [51] Waste cooking Multiwave PRO microwave Batch: 100 mL Box- Behnken design M:O- 7.46:1
oil reactor M:O- 6 – 9: 1 CaDG wt %- 1.03%
(continued on next page)

2
A. Sharma, et al. Renewable and Sustainable Energy Reviews 116 (2019) 109394

Table 1 (continued)

Author (Year) [Ref.No.] Feedstock Reactor Details Process Parameters Type of DOE Key Findings

Temp: 50–70 °C Temp: 62 °C

CaDG wt %- 0.5–1.25% 94.86% yield
Power: 850 W Time: 15 min
Pseudo 1st order reaction
Activation energy:
26.56 kJ/mol
Supraja et al. (2019) [81] Waste cooking – Esterification Central composite Esterification
oil O:M − 0.1 – 1 rotatable design M:O- 19.57:1
Time: 10–60 s Time: 35 s
Power: 100–400 W Power: 250 W
Transesterification FFA reduced: 0.082%
M:O-5:1 Transesterification
NaOH: 2 wt % Yield: 94.6%
Temp.: 65 °C
Time: 30 min
Selvaraj et al. (2019) [82] Waste cooking Domestic microwave oven KOH wt %: 0.5–1.5% Box-Behnken and 95% conversion
oil M:O – 3–9:1 Artificial Neural KOH wt %:1%
Time: 30–90 s Network M:O - 6:1
Temp.: 65–85 °C Temp. 75 °C
Time:60 s

M:O- Methanol: oil molar ratio, E:O- Ethanol: oil molar ratio, O:M − Oil: methanol molar ratio, Temp: Temperature, Cat%: Catalyst loading, FFA: Free fatty acid.

implementation of the policy decision of blended fuel [21]. Based on
the current estimates, about 75% of total manufacturing cost of bio-
diesel produced from fresh edible feedstock is 1.5 times higher than
commercial diesel [22] and further there is the concern of food security.
These problems can be reduced by using waste cooking oil (WCO) in-
stead of virgin vegetable oil, as the price of the former is 2–3 times
cheaper [23]. Utilization of WCO minimizes the environmental pollu-
tion by recycling the oil instead of disposing in landfills [24]. Thus,
biodiesel produced from WCO is gaining momentum in fuel and lu-
bricant market as a potential feedstock. According to the present world
scenario USA, Canada, UK and Europe are generating about 138, 0.135,
0.2 and about 1 million tons per year of WCO, respectively [25].
As per Indian financial express report of 2017 [26], about 1.2 mil-
lion ton cotton-seed oil is produced every year and nearly 60–65% of
total production takes place in Gujarat, India which will generate large
quantity of WCCO per year [27]. Biodiesel can be produced using lo-
cally available WCCO and it has a rising demand due to several ad-
vantages such as non-toxic, renewable, clean and environment friendly
fuel etc. [28–30].
Several researchers have reported their studies for biodiesel pro-
duction from WCO as a potential feedstock using conventional method
(mechanical stirring) [31–33]. Conventional method has limitations of
low conversion, slow and inefficient heating, excess quantity of re-
actants and high operating conditions like temperature and stirring
speed [30]. Thus, leading to excess consumption of energy for biodiesel
production. Apart from conventional method various process in-
tensification techniques used for biodiesel production are membrane
reactor [34], reactive distillation [35], ultrasonic and microwave irra-
diation (independent or in combination) [36–38]. Amongst them ul-
trasonic and microwave-assisted method significantly influences bio-
diesel yield. The ultrasonic method operates at low temperatures and
affects the heating at molecular level, thus saves the heating time [39].
The microwave method reduces the reaction time, thereby providing
fast and evenly distributed internal heating and ultimately improves the
separation steps [24,40]. Both these techniques are energy-efficient.
Non-ionizing nature of microwave radiations, influence molecular
motion, (dipole rotations) without changing the molecular structure.
Microwave irradiation accelerates molecular level heating of oil, me-
thanol and catalyst mixture [36]. Microwave heating demonstrates a
better option as the transfer of energy into a reaction mixture depends
upon thermal conductivity and convection currents of the mixture
[41,42]. Microwave method further helps to improve heat transfer ef-
fects resulting in shorter reaction time. The heat transfer dependent on
the ability of mixture to convert electromagnetic energy into heat [24].
However, microwave method is cost-intensive due to high capital cost
[39].
Design of experiment (DOE) is an effective tool for devising ex-
periments and data analysis to achieve the best yield with optimum
number of experiments [24]. Well-chosen method maximizes the in-
terference obtained from a given set of experimental runs [43]. The
commonly used DOE methods for biodiesel production include frac-
tional design [14], general full factorial design [44–47], Taguchi or-
thogonal array [48–50], Box-Behnken and central composite design
[51–53]. Full factorial design allows investigation of effect of all factors
to be estimated at all levels, providing information of influential
parameters over the prescribed range of experimental conditions [43].
The type of catalyst used for transesterification reaction to produce
biodiesel play an important role. There are various types of catalysts,
viz., acid, base, homogeneous, heterogeneous and ionic [52,54,55] used
for biodiesel production. Amongst them base catalyzed transesterifica-
tion is the most preferred catalyst as compared with other types which
are much slower in reaction [56]. Homogeneous catalyst provides a
higher yield with relatively less reaction time for biodiesel production.
But such catalysts are not eco-friendly as it cannot be recovered from
any of the products formed after transesterification reaction [57,58].
Compared to this, solid heterogeneous catalyst has regenerative capa-
city and reduced downstream processing [21].
The primary interest in operation of chemical reactions is to have
knowledge and understanding of chemical kinetics. It is important to
select an appropriate reaction method for safe and effective operation
[59]. Literatures on kinetic modeling using WCO with conventional
method for biodiesel production are a few [58,60–65]. Transester-
ification of waste frying oil was studied using calcined snail shell cat-
alyst. It was observed that the reaction followed first order kinetics with
activation energy of 79 kJ/mol [58]. Acid base catalyzed two step
transesterification of WCO using H2SO4 and NaOH was studied using
first order reaction and the estimated activation energy was found to be
88.76 kJ/mol [63]. Assuming pseudo first order reaction, kinetics of
overall process was described for CaO–ZnO catalyst transesterification
and the activation energy reported was 16.6 kJ/mol and 26.5 kJ/mol,
respectively for used vegetable oil and sunflower oil [64]. Transester-
ification of used cooking oil using mesoporous calcium titanate catalyst
was studied. Reaction found to follow pseudo first order kinetic with
21.25 kJ/mol activation energy [65].
Literature review of studies related to microwave-assisted method
for biodiesel production using WCO is summarized in Table 1.

3
A. Sharma, et al.
Outcomes of optimization and kinetic studies of referred work are also
mentioned. According to Table 1, a few studies have reported, only the
effect of microwave-assisted transesterification of different WCO.
Nevertheless, none of the studies compared the microwave-assisted
KOH and CaO catalyzed transesterification conditions related to process
optimization and kinetic modeling. Process optimization is required to
maximize biodiesel yield, whereas kinetic modeling is performed to
determine activation energy which is an important parameter for the
selection and design of biodiesel production. Due to the inherent fea-
tures of microwave-assisted method it is used for biodiesel production
in present work. Full factorial design method is applied to optimize the
process variables (methanol: oil ratio, catalyst loading, and reaction
time). Interaction effects of aforementioned process variables on the
biodiesel yield have been examined using RSM. The estimated physi-
cochemical properties of biodiesel are measured and compared with
that of ASTM standards.
The uniqueness of current study is application of microwave for
transesterification and its process optimization using WCCO. RSM
based full factorial design is applied for both KOH and CaO catalyzed
conditions to maximize biodiesel yield. The kinetic modeling was per-
formed to determine the activation energy which is an important
variable for biodiesel process design. Further scale-up and energy
analysis of the microwave-assisted transesterification process is also
performed. The application of microwave reactor substantially lowers
the activation energy and reaction time in comparison to conventional
method which makes the process energy-efficient as demonstrated in
this study.
2. Materials and methods
2.1. Materials and equipment
WCCO collected from local restaurant in Gandhinagar, India is used
for biodiesel production. Methanol (Emplura Grade), calcium oxide
(CaO) and calcium carbonate (CaCO3) powder (Emsure Grade) were
procured from M/s Merck, India. Potassium hydroxide (KOH) pellets
were procured from M/s. Fisher Scientific, India. The reaction was
performed in a microwave oven (Samsung conventional microwave
oven, 28l) with maximum power output of 900 W and frequency
2450 Hz.
2.2. Preparation and characterization of CaO catalyst
Five gram CaCO3 powder was used for calcination process. CaCO3
powder was heated in a muffle furnace from ambient temperature to
900 °C at a heating rate of 10 °C/min. At 900 °C it was kept for five
hours to complete the calcination reaction as shown in Eq. (1) [83].
CaCO3→CaO + CO2 (1)
Once prepared, CaO catalyst when exposed to air has a propensity to
convert into carbonate and hydrate. Hence, activation of catalyst prior
to experimental use is necessary [84]. Catalyst is further calcined for
reaction in a muffle furnace up to 700 °C for 2 h and kept in chamber till
the temperature achieves the ambient temperature. Catalyst is stored in
a vacuum desiccator to avoid moisture gain [85].
Analysis of CaCO3 and CaO was done using X-ray diffraction (XRD),
with PAN Analytica analyzer (X'Pert3 Powder). Samples were analyzed
using a double-crystal wide-anglegoniometry with the 2θ scan from 20°
to 80° at a scanning rate of 5° 2θ/min in 0.05° increments using CuKα
radiation (λ = 0.15406 nm).
2.3. Design of experiments (DOE)
The synthesis of biodiesel from WCCO using KOH and CaO cata-
lyzed condition was optimized using 33 full factorial design. Table 2
4
Renewable and Sustainable Energy Reviews 116 (2019) 109394
Table 2
Coded and real values of the factors selected for full factorial method.
Factors Levels for KOH Levels for CaO
−1 0 1 −1 0 1
M:O ratio (A) 6.0 8.0 10.0 8.0 10.0 12.0
Catalyst loading (w/w %) (B) 0.3 0.5 0.7 0.5 1.25 2.0
Reaction time (min) (C) 6.0 9.0 12.0 6.0 9.0 12.0
represents the coded and real values for lower (−1), medium (0) and
higher levels (+1) of factors used for the experiments with KOH and
CaO catalyzed conditions. Table 3 provides details of the total number
of experimental runs for factors, M:O ratio (A), catalyst loading (B) and
reaction time (C). Design-Expert® software (Version 10; Stat-Ease, Inc.,
USA) was used to prepare the DOE. Selection of real values for various
levels were decided based on initial trial experimental runs.
2.4. Transesterification reaction
Transesterification reaction was carried out using total batch size of
50 mL reaction mass in a flat bottom three neck flask (capacity: 250 mL)
fitted with a condenser and temperature sensor. Measured quantity of
preheated oil and pre-mixed mixture of methanol and catalyst were
added in a reaction flask for irradiation. A pulse power (half min cycle:
8 s on and 22 s off) of 180 W with slight stirring and reaction tem-
perature of 50 °C was maintained during all reaction runs. During each
run pH value was measured using a pH meter and was found to be in
the range of 7to 8 and 6 to 9 for KOH and CaO catalyzed conditions,
respectively. In KOH catalyzed condition upon completion of reaction,
two layers of reaction mass was observed, i.e. bottom layer of glycerol
and top layer of biodiesel with trace amount of unreacted oil and me-
thanol. Similarly, for CaO catalyzed condition, upon completion of re-
action formation of three layers was observed i.e. bottom most layer of
catalyst, middle layer of glycerol and the top most layer of biodiesel
with trace amount of unreacted oil and methanol. Upon separation of
glycerol layer and methanol recovery, biodiesel produced from KOH
catalyst was rinsed three times with deionized water to remove bits of
KOH catalyst. CaO catalyst was separated using a high speed centrifuge,
and after drying, reused without pretreatment or regeneration. Excess
methanol was separated from remaining liquid product. The biodiesel
rich phase was further washed with deionized water to remove traces of
unreacted oil and heated up to 80 °C in a rotary evaporator to remove
any traces of moisture. Experiment run under optimized conditions was
triplicated. The complete process is explained using a flow chart as
shown in Fig. 1.
2.5. Revalidation of full factorial optimized process parameters using
Taguchi orthogonal array method
Using Minitab statistical software (version 17), the Taguchi ortho-
gonal array method was applied to revalidate full factorial optimized
process parameters (i.e M:O ratio and catalyst loading) over a narrow
range. Optimized reaction time of KOH and CaO catalyzed conditions
was kept constant for all experimental runs. This highly fractional de-
sign was used to estimate the main effects using limited experimental
runs over a narrow range of levels, thus reducing the time and cost for
performance of experiments [50]. The nature of signal/noise (S/N)
ratio minimizes the negative effects of uncontrolled factors on proces-
sing and provides optimum condition for each parameter when the
level has a highest S/N ratio. Optimization was performed based on the
larger-the-better category [48]. Reaction temperature as a third para-
meter was included for optimization.
A. Sharma, et al. Renewable and Sustainable Energy Reviews 116 (2019) 109394

Table 3
Full factorial design matrix shows the experimental and predicted yield of biodiesel for KOH & CaO catalysts (highlighting the maximum and minimum yield).
Coded Factors KOH catalyzed conditions CaO catalyzed conditions

Run Factor A Factor B Factor C % Experimental Yield % Predicted Yield % Experimental Yield % Predicted Yield

1 0 0 1 93.89 93.49 90.50 87.85

2 0 −1 1 79.34 79.47 76.36 76.20
3 1 −1 1 83.87 82.94 76.45 75.83
4 1 −1 −1 71.09 72.23 65.49 65.00
5 0 0 0 93.87 94.31 89.94 90.67
6 −1 1 1 94.71 94.21 78.91 77.49
7 −1 0 −1 87.93 87.01 83.01 82.88
8 0 −1 −1 71.78 71.07 69.34 70.30
9 −1 −1 0 73.49 74.82 76.32 77.06
10 0 0 −1 86.21 87.51 81.19 81.05
11 1 −1 0 81.26 81.39 76.52 76.63
12 −1 −1 1 74.29 74.06 72.07 71.33
13 0 1 0 96.77 96.44 83.01 82.39
14 1 0 −1 87.67 86.06 75.17 74.48
15 1 1 0 94.02 93.55 78.91 78.20
16 −1 1 0 96.45 97.39 84.35 83.02
17 −1 −1 −1 67.89 67.97 71.34 70.36
18 0 −1 0 80.06 79.08 78.32 79.46
19 1 1 −1 86.84 86.80 62.62 64.96
20 0 1 −1 90.01 90.85 75.22 72.81
21 −1 0 0 94.06 92.65 89.06 89.54
22 1 1 1 92.70 92.68 78.59 77.59
23 1 0 0 93.71 94.02 86.92 86.56
24 1 0 1 92.89 94.35 84.13 86.21
25 0 1 1 94.75 94.41 77.89 80.51
26 −1 0 1 89.89 90.68 83.12 84.26
27 −1 1 −1 93.08 92.96 73.44 75.43

2.6. Method for analysis and characterization of WCCO and biodiesel
WCCO was characterized using gas chromatography-mass spectro-
scopy (GC-MS) [Agilent Inc. GC (7890A) and MS (5975C) having HP-
5MS capillary column (length - 30 m, diameter - 0.25 mm, film thick-
ness - 0.25 μm)] to find the fatty acid profile. Properties of WCCO such
as moisture content was determined using Karl Fisher titrator (model:
μAquaCal10; M/s Analab, Vadodara). Acid value and free fatty acid
content were analyzed using potentiometric titrator (model: 877 Titrino
Plus; M/s Metrohm, Switzerland). The various physicochemical prop-
erties of the WCCO biodiesel produced were measured. Bomb calori-
meter (model: C200, M/s IKA, China) was used to measure calorific
value of biodiesel. Closed cup Pensky-Martens equipment (model: PMA
5; M/s Anton Paar, Germany) was used to measure flash point as per
ASTM (D93) method. Viscosity of biodiesel at 40 °C is measured using
Brookfield viscometer (model: LVDV2T; M/s Brookfield USA) according

Fig. 1. Flow chart explaining biodiesel production using microwave irradiation and conventional method (For CaO catalyzed reaction one may observe third white
layer of catalyst in gravitation separation) [Catalyst: KOH/CaO, Impurities: Unreacted WCCO & traces of glycerol].

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A. Sharma, et al. Renewable and Sustainable Energy Reviews 116 (2019) 109394

to ASTM (D445) method. Density was determined using 10 mL gravity methanol is considered to be pseudo-first-order reaction. Equation (4)
bottle. Biodiesel samples were analyzed using in-house laboratory de- has been fitted for conversion vs. time to obtain kinetic rate constant
veloped GC method on GC-FID (Agilent Technologies, 5975C) having a [87].
flame ionization detector (FID) with HP-5MS capillary column.
− ln(1 − X ) = k ∗ t (4)
Temperature program for operation with an initial temperature at
−1
100 °C for 1 min increased to 160 °C at a rate of 20 °C/min for 5 min where, k is reaction rate constant (min ) and X is triglyceride con-
heating up to 240 °C with a rate of 5 °C/min, held for 5 min. Pure ni- version.
trogen gas was used as carrier gas. Injection was performed with split In order to determine activation energy Ea (kJmol−1), the Arrhenius
ratio of 100:1 and the sample size was 1 μl. Detector and injector equation (Eq. (5)) is used.
temperatures were set at 250 °C and 280 °C respectively. The identifi-
E
cation of FAME in a sample was performed by comparing the authentic k = A ∗ exp ⎛ a ⎞
⎜ ⎟

standard retention times. ⎝ Ru T ⎠ (5)

Yield for biodiesel prepared from both KOH and CaO catalyst was −1
where, A is pre-exponential factor (min ), T is reaction temperature
determined using Eq. (2) [16]: (K), Ru is universal gas constant (8.314 J/mol K).
Weight of Biodiesel Produced Eyring- Polanyi equation (Eq. (6)) was used to calculate thermo-
% YieldBD = × 100 dynamic behavior of transesterification reaction based rate constants
Weight of Raw Oil (2)
determined through kinetic study [65].
k ΔH k ΔS
2.7. Statistical multi regression analysis ln =− + ln b +
T Ru T h Ru (6)
Multiple regression analysis was performed on the experimental where, k is temperature dependent rate constant at temperature T, ΔH
data of FAME yield to fit the polynomial equation (second order) using and ΔS are the changes in enthalpy and entropy of activation (de-
analysis of variance (ANOVA). ANOVA is a well-established technique termined via slope and y-intercept respectively), kb is Boltzmann con-
to examine importance of an individual parameter as well as select stant and h is the Planck's constant. Additionally, Gibbs free energy
optimization model using a mathematical equation. Curvature as a re- (ΔG) was determined by Eq. (7).
sponse function could be modeled for three nominal factors with their (7)
ΔG = ΔH − TΔS
respective levels and the analysis of a quadratic relationship between
response and selected factor along with its interaction effect was ob-
tained. General regression model equation is as follows [53]: 2.9. Energy analysis for lab-scale experiments
k k
y = β0 + ∑ βjxj + ∑ βjjx2j + ∑ ∑ β ij x i x j + ε Power dissipation via microwave system was calculated applying
j=1 j=1 i <j=2 (3) standard calorimetric method which is based on the thermal energy
studies [88] for 50 mL batch size at nominal power of 180 W and
where, y is response, β0 constant coefficients, βj, βjj and βij represent the
500 mL batch sizes, at nominal power by applying 180 W and 450 W.
coefficients for linear, quadratic, and second order interaction effects,
Efficiency factor (η) can be calculated as ratio of energy input to
respectively. xj and xi represent the coded independent process variable
energy required at a specific temperature using Eq. (10). [89].
and ε represents standard error between the observed and model cal-
culated response value. Qth
η=
Qmw (8)
2.8. Kinetic modeling and thermodynamic studies where, energy supplied to microwave setup is energy dissipated in the
liquid mixture.
Kinetic modeling study on both catalyst conditions was carried out
under optimum process parameters obtained (i.e. M:O ratio and catalyst Qmw = Pmw t (9)
loading) from full factorial DOE for three temperatures i.e., 45 °C, 50 °C Qth = mCp ΔT (10)
and 55 °C. Samples taken at specified time were quenched immediately
to freeze the reaction and later analyzed to estimate the kinetic study where Qmw is energy input to microwave, Pmw is available microwave
parameters. The following assumptions were made for kinetic study: i.) power, Qth is energy required to reach a certain temperature, m is mass
Change in concentration of catalyst and possibility of reverse reaction of sample, Cp is speific heat capacity of oil and methanol mixture, ΔT is
are ignored by using sufficient quantity of catalyst, ii.) Reaction being difference in initial and final temperature of mixture.
batch type, reaction mixture and catalyst distribution are uniform, iii.)
Constant methanol concentration is considered during reaction, iv.) 3. Results and discussion
Intermediate reagents produced during reactions were neglected, v.)
Reaction shown in Fig. 2 was assumed to be irreversible pseudo 3.1. XRD analysis of CaO
homogeneous function of oil concentration [86,87].
Kinetics of transesterification reaction in the presence of excess It can be seen from Fig. 3 that XRD confirms the complete phase

Fig. 2. Stoichiometric transesterification reaction for biodiesel production.

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A. Sharma, et al. Renewable and Sustainable Energy Reviews 116 (2019) 109394

3.3. Analysis of variance (ANOVA)

Using Design Expert®, statistical analysis was performed according

to DOE mentioned in Table 3. The maximum and minimum yield (%)
achieved using KOH and CaO were 96.77 and 90.5%, and 67.89 and
62.62%, respectively. Using the yield data of Table 3, ANOVA tech-
nique was employed to investigate the regression model significance at
95% confidence level.
The mathematical relationship between independent variables and
dependent response is represented by coded terms in Eq. (11) and Eq.
(12) for KOH and CaO catalysts respectively.

yKOH = 94.31 + 0.68A + 8.68B + 2.99C − 2.60AB + 1.16AC − 1.21BC

− 0.97A2 − 6.55B2 − 3.81C 2 (11)

yCaO = 90.87 − 1.39A + 1.71B + 3.4C − 1.28AB + 2.31AC + 0.45BC

− 2.92A2 − 9.50B2 − 6.21C 2 (12)

Fig. 3. XRD spectrum of calcium carbonate (CaCO3) and prepared calcium
oxide (CaO) catalyst showing the phase transformation peaks.
transformation of CaCO3 yielding to CaO. This is verified by observing
the 2θ values at 33.2°, 37.03°, 54.07°, 62.1° and 65.34°, corresponding
to (111), (200), (202), (311) and (222) planes respectively, occur
during calcination. The obtained results are in agreement with the
standards (JCPDS file no. 061550) and the findings reported in litera-
ture [90]. The main signature peak after calcination for CaO is at a 2θ°
value of 37.03° and similar result was found in literature [83].
3.2. Characterization of WCCO
Fatty acid composition of WCCO was analyzed using gas chroma-
tography and found to contain 0.99% myristic acid; 28.65% palmitic
acid; 0.97% palmitolic acid; 2.55% stearic acid; 24.69% oleic Acid;
40.88% linoleic acid and 1.27% linolinic acid. According to this ana-
lysis, palmitic acid (C16H32O2; C16:0; saturated), oleic acid (C18H34O2;
C18:1; monounsaturated) and linoleic acid (C18H32O2; C18:2; poly-
unsaturated) are the major components in WCCO. The amount of acids
obtained to confirm WCCO are within range as reported in literature
[91,92]; saturated acid (26–35%), monounsaturated acid (18–24%) and
poly unsaturated acid (42–52%). Observed acid value of WCCO was
1.78 mg KOH/g which corresponds to free fatty acid content of 0.89%,
considered as suitable for single step conversion to biodiesel. Estimated
moisture content was found to be less than 0.05%.
From Eqs. (11) and (12) it is observed that linear terms have a
positive effect on the yield except M:O ratio (A) in case of CaO catalyst
condition. With change in linear terms the yield changes as a function
of its coefficients. The quadratic terms with negative sign have a ne-
gative effect on the yield, which means that with an increase in the
quadratic coefficient values the % biodiesel yield will decrease. For Eq.
(11), the interaction terms (AB, BC, and AC) have a mixed response
over the % biodiesel yield. The terms having interaction of catalyst
loading (B) will reduce the % biodiesel yield if the value is increased or
decreased from the mid-level; whereas interaction between M:O ratio
and time shows positive response. Similarly, in Eq. (12) the interaction
term (AB) indicates negative response, and interaction terms AC and BC
show positive effect on the biodiesel yield with increase in these
quantities. Negative quadratic terms in both equations show that the
decrease in yield is found to be in quadratic manner.
ANOVA results are tabulated in Table 4 for KOH and CaO catalyzed
conditions respectively. Model row shows the amount of variations
explained by the model along with overall model test of significance. In
this study, for both the catalyst conditions, the model selected for
analysis is significant as the p-values are less than 0.0001. The sig-
nificance of particular process parameter is proved by its p-value having
magnitude below 0.05. Residual row shows the amount of response
(mean square values) which is still unexplained by the model. The
analysis focuses on the mean of performance characteristics which is
achieved by evaluating Fischer's test value (F-value). The F-values of
model 207.59 for KOH and 45.01 for CaO and its p-values being <
0.0001 indicates it is significant model. Thus, the model is proven to be
significant for optimizing the transesterification of WCCO within pre-
scribed levels of process parameters. The significance of p-value sig-
nifies error probability involved to examine regression coefficient's

Table 4
Analysis of variance (ANOVA) for biodiesel production using KOH and CaO catalyst (Significant terms are highlighted).
KOH catalyst system CaO catalyst system

Source of Variation Degree of Freedom Sum of Squares Mean Square F-value p-value Sum of Squares Mean Square F-value p-value

Model 9 1990.55 221.17 207.59 < 0.0001 1205.42 137.77 45.01 < 0.0001
A - M:O 1 8.35 8.35 7.84 0.0123 34.72 34.72 11.67 0.0033
B - Catalyst % 1 1356.51 1356.51 1273.23 < 0.0001 52.46 52.46 17.63 0.0016
C - Time 1 160.98 160.98 151.10 < 0.0001 208.08 208.08 69.92 < 0.0001
AB 1 81.28 81.28 76.29 < 0.0001 19.53 19.53 6.56 0.0202
AC 1 16.03 16.03 15.05 0.0012 64.22 64.22 21.58 0.0002
BC 1 17.55 17.55 16.47 0.0008 2.43 2.43 0.82 0.3788
A2 1 5.68 5.68 5.34 0.0337 51.20 51.20 17.2 0.0007
B2 1 257.15 257.15 241.37 < 0.0001 541.06 541.06 181.82 < 0.0001
C2 1 87.02 87.02 81.68 < 0.0001 231.72 231.72 77.87 < 0.0001
Residual 17 18.11 1.07 50.59 2.98
Total 26 2008.66 1256.01
R2 = 99.10%, Adj R2 = 98.62% R2 = 95.97%, Adj R2 = 93.84%

7
A. Sharma, et al.
significance and interaction effect of each cross product.
For KOH catalyst condition the linear, quadratic and interaction
terms are significant. Similarly, for CaO catalyst condition, all linear,
quadratic and interaction terms are significant except interaction term
between catalyst loading (B) and reaction time (C). As per the ANOVA
Table 4, for both catalyzed conditions M:O ratio has the highest p-va-
lues and lowest F-values, hence it is the lowest significant parameter
among the three factors (M:O ratio, Catalyst loading and Reaction
Time).
The coefficient of determination (R2) in Table 4 reveals the varia-
bility of the dependent variable by its relationship with the independent
variables (predictor variables). Good fit between the model and ex-
perimental data is indicated by the higher value of R2. It can be seen
from Table 4 that the R2 values are 99.10% and 95.97% for KOH and
CaO catalyzed conditions respectively. This means the model does not
explain 0.9% and 4.03% variation in experimental data respectively, for
KOH and CaO catalyzed conditions ensuring high accuracy between
model prediction and experimental data. Similar R2 results were found
in literature for homogeneous and heterogeneous catalysts having the
range of 98.35–99.72% [51,79,80].
The amount of reduction in variability of yield obtained by using
variables in model is measured by R2. Larger value of R2 does not al-
ways implies that the model is the best fit [24]. Adding variable will
always increase R2 value, regardless of whether the variable is sig-
nificant or not. Compensation for this undesirable effect is done by
adjusting the coefficient of determination (adjusted R2) by not only
explaining how well the model is fit but also accounts for a predictor
variables number. The adjusted R2 will increase if only significant
predictor variables are added into the model [43]. In this study, 98.62%
for KOH and 93.84% for CaO conditions were the adjusted R2 values.
As seen from Fig. 4(a) and (b), predicted yield values were con-
sistently distributed along the diagonal and near the actual responses.
This shows that the ANOVA generated regression model can adequately
explain the relationship between independent variables and biodiesel
yield. Model predicts data points within ± 5% error limit showing ex-
cellent stability of regression model.
Fig. 5(a) and (b) exhibit relation between yield residuals and their
normal distribution which follows a straight line for KOH and CaO
catalyzed conditions. The plot shows that all the data points are nor-
mally distributed as it is closely aligned to the reference line, allowing
the test for the model to be significant. Reference line gives the ex-
pected values of predicted and experimental yield if the data follow
exact normal distribution.
Perturbation plots (Fig. 6 (a) and (b)) helps in identifying the order
of each process variable and its effect while keeping the other process
variable constant [24]. The sensitivity of factors A (M:O ratio), B
(catalyst loading) and C (reaction time) on the biodiesel yield is
Fig. 4. Comparison of predicted versus experimental biodiesel yield% values within ± 5% confidence interval for (a) KOH and (b) CaO catalyzed conditions.
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Renewable and Sustainable Energy Reviews 116 (2019) 109394
reflected by the nature of the curvature. The factor with steeper slope
has more pronounced effects on biodiesel yield as compared to flatter
slope [93]. Hence, the plot depicts that factor B has prominent effect on
biodiesel yield for both KOH and CaO catalyzed conditions followed by
C and A similar to that reflected in Table 4 of ANOVA. Fig. 6(a) shows
that catalyst loading (B) at the lower level till the middle value is more
sensitive, whereas the sensitivity reduced between middle to higher
level. Fig. 6(b) shows that the catalyst loading (B) is most sensitive on
either side of mid-level. It is worth mentioning that as per the ANOVA
analysis, catalyst loading (B) is the most significant factor, followed by
reaction time (C) and M:O ratio (A) for both catalyzed conditions. Thus,
perturbation plots reiterate the findings of ANOVA analysis.
In order to have a detailed understanding of the process parameters
individual and interaction effects of all these parameters on biodiesel
yield has been discussed in subsequent section. These plots conclude
good predictability of the observed model for optimization.
3.4. Individual parameter effect on biodiesel yield
Individual parameter effect plots (Fig. 7 a-f) are formed by keeping
only one factor as variable and other two kept fixed at zero level (i.e.
middle level). Experimental values are shown at the three levels in
comparison to the predicted value in plots. In the present study, three
individual parameters considered are M:O ratio (A), catalyst loading (B)
and reaction time (C).
3.4.1. Effect of M:O ratio
Fig. 7(a), shows variation in yield with respect to M:O ratio. The
yield varies from 6:1 to 10:1 maintaining the catalyst loading and re-
action time by 0.5% and 9 min. Yield at the lowest level (6:1) was
observed to be 92.65% and highest yield of 94.42% was observed at
8.7:1 ratio. The biodiesel yield reduced to 94.02% with increasing M:O
ratio (10:1). The trend of the plot is almost horizontal with slight bends
at the end values showing M:O ratio to be the least significant thereby
supporting the ANOVA analysis in Table 4. Suitable quantity of M:O
ratio is required as it increases the solubility of KOH catalyst aiding the
forward movement of reaction [24].
In Fig. 7(b), M:O ratio varies from 8:1 to 12:1, maintaining the
catalyst loading and reaction time at 1.25% and 9 min, respectively.
Predicted biodiesel yield is 86.62% and 89.34% respectively at highest
and lowest level of M:O ratio. The maximum yield observed is 91.03%
at 9.5:1 M:O ratio. The trend in the plot of Fig. 7(b) shows that increase
in M:O ratio from lowest level (−1) to middle level (0) causes an in-
crease in yield, whereas a further increase in molar ratio (middle to
highest level) reduced the yield %.
For both KOH and CaO catalyzed conditions, the M:O ratio is taken
more than the stoichiometric ratio and hence for respective catalyst
A. Sharma, et al.
Fig. 5. Normal % probability plot versus residual plot for experimental biodiesel yield for (a) KOH and (b) CaO catalyzed conditions.
loading at the high level the yield decreases. Excess use of methanol
was not appreciated in case of heterogeneous catalyst as well.
Increasing the M:O ratio beyond a certain value increases the glycerol
solubility leading to foam formation and lowering the yield [74]. The
experimental yield data points indicated on the plots validate the trend
and the predicted values.
3.4.2. Effect of catalyst loading
Fig. 7(c) and (d), show the effect of catalyst loading over biodiesel
yield for KOH and CaO conditions, respectively. For KOH (Fig. 7(c)),
the catalyst loading varied from 0.3 to 0.7%, while maintaining the M:O
ratio and reaction time with their middle values. Predicted biodiesel
yield is 79.31% and 96.44% respectively at the lowest and highest level
of catalyst loading. The maximum yield observed is 97.18% at 0.63%
catalyst loading.
The plot shows that biodiesel yield is very sensitive between the
lower and middle level of catalyst loading. After achieving the max-
imum yield at middle level, it starts decreasing in the highest level.
Excessive use of KOH catalyst loading results in formation of soap and
separating glycerol and biodiesel becomes difficult [24]. Fig. 7(d), the
CaO catalyst loading plot shows a very steep drop in yield of 79.66%
and 83.08%, respectively at lower level and higher level and it shows
catalyst loading to be highly sensitive to biodiesel yield. Highest bio-
diesel yield of 90.94% was observed at 1.32% catalyst loading near the
Fig. 6. Perturbation plot showing significant parameter affecting biodiesel yield% for (a) KOH and (b) CaO catalyzed conditions with factors M:O ratio (A), Catalyst
loading (B) and Reaction time (C) with actual intermediate level values.
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Renewable and Sustainable Energy Reviews 116 (2019) 109394
middle level. Excessive amount of heterogeneous catalyst increases
washing time and decreases formation of biodiesel as reactant mixture
becomes more viscous and thus, increases mass transfer resistance [94].
Suitable amount of catalysts reduces catalyst waste and avoids pollution
of water bodies.
3.4.3. Effect of reaction time
Fig. 7(e) and (f) show the variation of yields with respect to reaction
time. For both catalyst conditions the yield increases between lower
and middle level and after achieving the maximum values, 93.52% at
10.19 min for KOH and 91.33% at 9.8 min for CaO between middle and
high level it further decreases with increase in time.
Yield at lower reaction time is lesser because of the presence of
unreacted oil in the reaction mixture that makes the reaction in-
complete. Very high reaction time increases temperature of the system
causing excessive evaporation of methanol. It also causes damage to the
molecules, thus initiating reverse (backward) reaction [75].
Analysis of the individual process variable effect brings a valuable
understanding about how each parameter affects the yield of biodiesel.
However, it does not provide a broad view on how the interactions
among variables affect the yield. Thus, it is required to study the three-
dimensional surface plots and two-dimensional contour plots of pre-
dicted biodiesel yield (%) which are drawn by keeping the middle level
value constant. The interaction plots provide a clear insight about the
A. Sharma, et al. Renewable and Sustainable Energy Reviews 116 (2019) 109394

Fig. 7. Individual parameter effect plots based on ANOVA for process parameter M:O ratio, catalyst loading and reaction time indicating significance of each
parameter from low to high level on the biodiesel yield% for KOH (a, c, e) and CaO (b, d, f) catalyzed conditions with 95% confidence interval band for constant
actual factors.

reaction hence they are more important than single parameter plots. ratio does not favour biodiesel production as separation becomes dif-
ficult. Hence, the yield seems to reduce slightly. A similar trend is ob-
served in the literature where excess alcohol ratio causes difficulty in
3.5. Interaction parameter effect on biodiesel yield
separation [69]. Methanol enhances transesterification reaction as it is
a good microwave radiation absorption material having dipole re-
Fig. 8(a), shows M:O ratio and catalyst loading interaction having a
orients [71]. Hence, even with higher amount of methanol the yield is
reaction time constant at 9 min. The plot shows a trend that up to 0.5%
above 95%. The lower amount of catalyst loading may not be favour-
catalyst loading with 8.3:1 M:O ratio the yield is less than 95%. The
able as the catalyst may not be able to take the reaction in forward
yield contours show a highest value (96.44%) when the M:O ratio is
direction as it will not be able to overcome the heat barrier required for
kept below 9:1 and catalyst loading has increased more than 0.6%. If
the reaction to move further.
M:O ratio is increased beyond 9:1 with even higher catalyst loading, the
Fig. 8(b) shows the effects of M:O ratio to reaction time with
yield tends to decrease, though it stays above 95%. Excess M:O molar

10
A. Sharma, et al.
Fig. 8. Three dimensional response surface and contour plots showing the interaction effect of (a) M:O ratio to catalyst loading, (AB) (b) M:O ratio to reaction time,
(AC) (c) reaction time to catalyst loading (BC) on biodiesel yield% for KOH catalyzed condition.
constant catalyst loading (0.5%) at middle level. The plot is almost flat,
showing more than 90% biodiesel yield, which is obtained at more than
6.7 min of reaction time for the entire range of M:O ratio. But to in-
crease the yield above 95%, M:O ratio required is more than 8:1 and
reaction time is between 9.6 and 11.2 min. Constant middle value of
0.5% catalyst loading seems to be favourable for transesterification
reaction as more than 90% biodiesel yield is obtained over the entire
selected range of M:O ratio with overall reaction time above 6.7 min.
Fig. 8(c) shows the effect of catalyst loading and reaction time with M:O
ratio fixed at the middle level (8:1). Biodiesel yield below 0.4% catalyst
loading is less than 90% for the entire range of reaction time selected.
More than 95% biodiesel yield is observed when catalyst loading is
more than 0.5% and reaction time is above 7.3 min. As stated above,
the amount of catalyst loading more than 0.5% is favourable for the
reaction to proceed forward after 7.3 min. Very high amounts of cata-
lyst tends to have saponification which reduces the yield and also in-
creases complexity in product separation [20].
Optimized values for process parameters are 7:1, 0.65 (w/w) % and
reaction time 9.6 min, respectively for M:O ratio (A), catalyst loading
(B) and reaction time (C) in KOH catalyzed conditions. The predicted
yield at optimum conditions was 96.44%. The average maximum yield
achieved at optimum condition was 96.55 ± 0.23%.
Fig. 9(a), shows M:O ratio and catalyst loading interaction with
reaction time as constant middle value (9 min). The elliptical plots here
show a possibility of good interaction between the reaction parameters.
For catalyst loading between 1 and 1.6%, the yield of biodiesel is more
than 90% for a wide range of M:O ratio (8.2:1 to 10.7:1). For upper and
lower ranges of catalyst loading, the trend shows a reduction in the
yield of biodiesel below 90%. The plot shows catalyst loading near the
middle level to be effective enough to interrupt the heat barrier and
move the reaction in forward direction for M:O ratio up to 10.7:1 with
overall reaction time of 9 min. Lower catalyst loading leads to
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Renewable and Sustainable Energy Reviews 116 (2019) 109394
unsatisfactory conversion yield whereas higher amount results in
higher mass transfer resistance causing slower reaction rates because of
formation of slurry [80,94].
Fig. 9(b), shows M:O ratio to reaction time interaction having the
constant middle value of catalyst loading (1.25%). More than 90%
biodiesel yield is obtained in the range of M:O ratio 8.3 to 11.1: 1 and
reaction time 8.2–11.2 min. The plot depicts that 1.25% of catalyst
loading at 50 °C is enough to achieve the yield of 90%. It was observed
that a longer duration of the microwave irradiation ensures better ex-
posure of the reaction mixture to irradiation. This could be due to in-
tensification of contact between reacting materials by inducing thermal
effect [95].
Fig. 9(c), shows interaction between catalyst loading and reaction
time with a hold value of M:O ratio (10:1). For catalyst loading ranging
from 1 to 1.6% the yield is more than 90% having a reaction time
between 8.4 and 11.2 min. Catalyst loading and reaction time outside
this range shows reduction in biodiesel yield (< 90%). This could be
because a heterogeneous catalyst requires time to mix properly with the
reaction mixture and once the reaction is started it progresses with
time. But it can be noted that with 10:1 M:O the yield drops on either
ends of 1–1.6% catalyst loading which can be due to longer exposure of
catalyst with methanol that reduces the quality of catalyst. If the re-
action time crosses 12 min, it was observed that solvent losses were
higher and that there was overheating of reaction medium [79]. As
described earlier the interaction is insignificant as per ANOVA Table 4
and it can be seen in the plot as the amount of catalyst loading remains
between 1 and 1.6% for a wide range of reaction time change.
Optimized values for process parameters are 9.6:1, 1.33 (w/w) %
and reaction time 9.7 min, respectively for M:O ratio (A), catalyst
loading (B) and reaction time (C) in CaO catalyzed conditions. The
predicted yield at optimum conditions was 89.94%. The average max-
imum yield achieved at optimum condition was 90.41 ± 0.02%.
A. Sharma, et al. Renewable and Sustainable Energy Reviews 116 (2019) 109394

Fig. 9. Three dimensional response surface and contour plots showing the interaction effect of (a) M:O ratio to catalyst loading (AB), (b) M:O ratio to reaction time
(AC), (c) reaction time to catalyst loading (BC) on biodiesel yield% for CaO catalyzed conditions.

3.6. Revalidation of optimized results using Taguchi method Table 6

Taguchi design matrix for KOH and CaO catalyzed conditions.
Table 5 shows the parameters selected for performing the re- Coded Factors Experimental Experimental
validation experiments using Taguchi method for KOH and CaO cata- Run Yield Yield
lyzed conditions. Level values were selected based on the optimized
results obtained using full factorial method (discussed in Section 3.5) A B D KOH CaO

The optimized condition was selected as the middle level values, 1 −1 −1 −1 96.01 89.00
whereas assigned upper and lower levels have been shown in Table 5. 2 −1 0 0 96.53 90.50
Instead of reaction time, reaction temperature was selected as the third 3 −1 1 1 96.09 90.05
factor. Reaction time was kept constant at 9.6 and 9.7 min, respectively 4 0 −1 0 96.17 90.23
5 0 0 1 96.40 90.03
for KOH and CaO catalyzed conditions. Table 6 was produced using
6 0 1 −1 96.38 90.08
MINITAB statistical software (version 17) which shows the number of 7 1 −1 1 96.20 90.10
runs and respective biodiesel yield for both the catalyzed conditions. 8 1 0 −1 96.11 90.13
According to Fig. 10 (a and b), all the parameters show S/N ratio 9 1 1 0 96.05 89.80
higher at middle level as compared to lower and higher levels. Hence,
the nature of S/N ratio variation revalidate the optimized process
variables assigned at middle level. It was observed that S/N ratio of 3.7. Catalyst reusability
catalyst loading parameter has the highest value as well as steepest
slope, which reconfirms the fact that it is the most sensitive parameter. Reusability of heterogeneous catalyst is an essential and advanta-
Thus, results of Taguchi method revalidates the optimum results ob- geous aspect in transesterification process. Reusability of CaO catalyst
tained by full factorial design using ANOVA. was studied up to 5 cycles under optimum reaction condition (refer
Section 3.5). It was observed that up to four cycles the biodiesel yield
achieved was more than 90%. The yield reduced less than 90% during
the fifth cycle. After each reaction cycle, the catalyst was recovered by
filtration from the reaction mass. Catalyst was then rinsed with me-
Table 5 thanol to clear adsorbed reactants and reused after post drying. Roschat
Coded and real values of the factors selected for validation using Taguchi et al. [96] has reported the similar results as mentioned above.
method.
Factors Levels (KOH) Levels (CaO)
−1 0 1 −1 0 1 3.8. Comparison of biodiesel yield for microwave and conventional method

M:O ratio (A) 6.5 7.0 7.5 9.1 9.6 10.1

The optimized parameters of microwave-assisted biodiesel pro-
Catalyst loading (w/w %) (B) 0.6 0.65 0.7 0.8 1.3 1.8
Temperature (°C) (D) 40 50 60 40 50 60 duced using KOH and CaO catalyzed conditions are described in Section
3.5. These optimized parameters were used in conventional method

12
A. Sharma, et al.
Fig. 10. Taguchi design to show the mean of signal to noise ratio versus process parameter (M:O ratio, catalyst loading, reaction temperature) for KOH and CaO
catalyzed conditions.
having a stirring speed of 400 rpm for biodiesel production. In con-
ventional method, biodiesel yield achieved was 48.19% and 36.20%
respectively for KOH and CaO catalyzed conditions. These yield values
are significantly lower than those obtained using microwave-assisted
transesterification. It is found that more than 90% biodiesel yield was
observed in conventional method, when the reaction time was extended
up to 40 min. Similar result was reported by Ref. [41] where 87%
biodiesel yield was obtained after 30min of reaction using NaOH cat-
alyst at 60 °C reaction temperature.
3.9. Analysis of kinetic modeling
Eq. (4) was applied to study pseudo first order reaction kinetics of
KOH and CaO catalyzed conditions. The temperature was increased
from 45° to 55 °C. Reaction rate constant (k) for transesterification re-
action was found to increase from 0.2924 to 0.3401 min−1 for KOH
catalyst and from 0.1813 to 0.2532 min−1 for CaO catalyst condition.
R2 value was more than 95% for both conditions. Various literatures
made the use of pseudo first order kinetics as the best fit for both types
of catalysts [64,97]. The activation energy, calculated using Eq. (5) as
shown in Fig. 11 for microwave-assisted transesterification was found
to be 13.05 and 28.93 kJ mol−1 for KOH and CaO respectively.
For conventional method experiments were performed to verify the
reaction kinetic assuming pseudo first order kinetic. The optimized
conditions obtained in Section 3.5 were used for this analysis. The ac-
tivation energies for conventional method using KOH and CaO cata-
lyzed conditions were found to be 34.5 and 50.4 kJ mol−1, respectively.
Thus, it can be concluded that reduction in activation energy using
microwave-assisted method was compared to conventional method is
Fig. 11. Arrhenius plot between ln (k) versus 1/T for estimation of activation
energy as per pseudo first order kinetic for KOH and CaO catalyzed conditions.
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Renewable and Sustainable Energy Reviews 116 (2019) 109394
62.4% and 42.6% respectively for KOH and CaO catalyzed conditions.
In comparison to literature the activation energy using microwave-
assisted method improves for both homogeneous and heterogeneous
catalysts [73,98]. Thus, reduction in activation energy with respect to
the conventional method is the result of presence of dipolar molecules
in presence of electric field. It causes non-thermal effects in the mi-
crowave and enhances the reactivity [99,100]. Hence, it proves the
effectiveness of microwave-assisted method in order to enhance the
reaction rate and reduction in reaction time.
3.10. Thermodynamic analysis
Table 7 shows details of ΔH, ΔS and ΔG values which were calcu-
lated using Eq. (7) and obtained from Fig. 12. The ΔH (enthalpy) with
positive value indicates the heat required to bring the reactants at
transition state and aid formation of products whereby the nature of
reaction becomes endothermic. The ΔS (entropy) with negative value
indicates the entropy of activation leading to decrease in transition
state having a formation of single active bond of two reactants where
the bonds are more structured at the ground state. The ΔG with positive
value indicates the reaction is not spontaneous and endergonic in
nature [101–104].
The scale-up study with tenfold increase in sample size (500 mL)
was performed as shown in Fig. 13 (a and b) for both the catalyzed
conditions. The optimum values of M:O ratio and catalyst loading was
used during transesterification reaction. The cycle time was 30 s (8 s on
and 22 s off for 180 W and 15 s on and 15 s off for 450 W). It was found
that for same microwave power input (180 W) the reaction time ob-
served were 10 and 20 min for 50 and 500 mL size, respectively to
obtain more than 90% yield in both catalyzed conditions. For KOH
catalyst, with increase in microwave power input (450 W) the reaction
time is reduced by 5 min compared to that of 100 W to achieve 90%
yield. Thus higher input is required to reduce the reaction time. The
effect of variation of microwave power input on biodiesel was studied
by Ref. [105] and reported similar results. As mentioned in Ref. [106]
biodiesel yield of 98% was achieved for 3 kg batch size using 600 W of
continuous multimode microwave. The effect of increase of power
output on reaction time was insignificant for 500 mL sample size in CaO
catalyst.
Table 7
Thermodynamic parameters for KOH and CaO catalyzed transesterification
reaction for biodiesel production.
Thermodynamic ΔH (kJ/ ΔS (kJ/ ΔG (kJ/mol)
Parameters mol) mol.K)
318 K 323 K 328 K
Values (KOH condition) 26.3 −0.17 80.36 81.21 82.06
Values (CaO condition) 10.4 −0.22 80.36 81.46 82.56
A. Sharma, et al. Renewable and Sustainable Energy Reviews 116 (2019) 109394

Table 8
Energy analysis for microwave and conventional transesterification method for
50 and 500 mL batch sizes.
Parameters Nominal power: 180 W Nominal power: 450 W

KOH CaO KOH CaO

50 mL 500 mL 50 mL 500 mL 500 mL 500 mL

Microwave-assisted transesterification
Energy dissipation, 1.00 11.00 1.20 11.97 18.33 19.96
(Qth,Wh)
Delivered energy, 5.8 51.23 5.8 51.23 88 88
(Qmw,Wh)
Efficiency factor 0.17 0.21 0.21 0.23 0.21 0.23
Biodiesel produced, 48.3 456 42.1 452 452 444
(mL)
Conventional method transesterification
Energy dissipation, 0.50 – 0.60 –
(Wh)
Delivered energy, 60 – 60
(Wh)
Efficiency factor 0.008 0.010
Fig. 12. Determination of thermodynamic parameters (enthalpy (ΔH) and en- Biodiesel produced, 24.4 18.1
tropy (ΔS)) using Eyring–Polanyi plot between ln (k/T) versus 1/T for KOH and (mL) at 10 min
CaO catalyzed conditions. Biodiesel produced, 44.8 – 41.6
(mL) at 40 min

3.11. Energy analysis

Table 9
Table 8 shows the comparison of energy consumption for micro- Comparison of fuel properties of produced biodiesel with ASTM D6571 stan-
wave reactor and conventional method during transesterification pro- dards.
cess. Energy dissipation in liquid mixture and efficiency factor were
Properties Biodiesel This Experimental Study
calculated by using Eqs. (10) and (8) respectively. The delivered energy
to the set-up was directly measured using energy meter. Efficiency ASTM Biodiesel Biodiesel (CaO)
factor increases with increase in sample size for both catalyzed condi- Standards (KOH)
tions. Thus, microwave method has potential for scale-up as desired for
Density, (kg/m3) 860 – 900 870 879
industrial application. Further efficiency factor value for conventional
Flash Point, (°C) > 130 183 176
method is very low in comparison to that of microwave method. Thus it Calorific Value (MJ/kg) 35 – 45 36.6 ± 2 38 ± 2
can be concluded that microwave method is highly energy-efficient Kinematic Viscosity, at 40 °C 1.9 – 6 4.2 ± 3 5.5 ± 3
than conventional method. (mm2/s)
Oxidation Stability, at 110 °C Min 3 10 10.4
(hours)
4. Fuel properties of product biodiesel Acid Value, (mg KOH/g) Max 0.5 0.34 0.48

Fuel properties such as density, kinematic viscosity (at 40 °C), flash

point, acid value and calorific value of biodiesel were measured as per
ASTM (D6751). The measured physicochemical biodiesel properties are
given in Table 9. All the property values lie within the prescribed ASTM
biodiesel limits, and can be used as an alternative fuel blended with
gasoline diesel.
5. Conclusions
In this study, microwave-assisted transesterification process was
successfully demonstrated to produce biodiesel from WCCO using KOH
and CaO catalyzed conditions. Optimum conditions for process para-
meters (M:O ratio, catalyst loading and reaction time) were determined
using RSM based full factorial design method. At optimum conditions of
the transesterification process, the regression model predicts the bio-
diesel yield within ± 1% marginal error. In reference to process para-
meters, it is found that biodiesel yield was highly sensitive to catalyst
loading followed by methanol: oil ratio and reaction time. Further,
studies focusing on individual and interaction effect of process

Fig. 13. Variation of biodiesel yield for scale-up study using (a) KOH (b) CaO catalyzed conditions.

14
A. Sharma, et al.
parameters are analyzed to exhibit the benefits of microwave-assisted
biodiesel production. Application of Taguchi orthogonal array method
was demonstrated to revalidate the optimized conditions. The micro-
wave-assisted method greatly accelerates the transesterification reac-
tion rate which significantly curtails the reaction time compared with
conventional method. Based on pseudo first order kinetic modeling, the
activation energy was experimentally determined. It was found that the
activation energy for microwave-assisted method is significantly lower
as compared to that of conventional method for both catalyzed condi-
tions. The scale-up study was performed with tenfold increase in batch
size than that of lab scale. The present microwave-assisted method has
shown potential for scale-up and therefore can be used for commercial
applications with suitable modifications. Reusability of CaO catalyst
was examined. It was observed that catalyst activity remains unaffected
up to four cycles. Energy analysis showed that energy consumed by
microwave-assisted method is energy-efficient compared to that of
conventional method. Physicochemical properties of produced bio-
diesel satisfies the fuel specifications designated as per ASTM D6751.
It can be concluded that observed results and optimized conditions
for microwave-assisted transesterification process were superior to that
of conventional method and indicate potential for saving of energy and
raw materials. The current study can be extended further by modifying
the existing microwave set-up. The possible modifications can be (i)
using the microwave in a loop for continuous production, (ii) using
multi-mode microwaves with larger capacity instead of the single-mode
and (iii) combining microwave irradiation with any other process in-
tensification technique. A detailed economic and environmental ana-
lysis is further needed prior to commercialization of microwave-assisted
biodiesel production process. The benefits of microwave as process
intensification technique has been well realized in the recent years,
especially for biodiesel production. It is essential that future studies
should focus on reactor design, magnetron modification and process
chemistry using new solvent combinations to improve the energy-effi-
ciency as well as the product cost.
Acknowledgments
The authors would like to thank the funding agency Gujarat Energy
Development Agency (GEDA), Gujarat, India for providing grants and
Centre for Biofuels and Bioenergy Studies (CBBS) in PDPU for providing
laboratory facilities for perform characterization and property estima-
tion.
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