Analytical Chemistry Letters

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Analysis of RSM Based BBD and CCD Techniques

Applied for Biodiesel Production from Waste
Cotton-Seed Cooking Oil via Ultrasound Method

Suvik Oza, Pravin Kodgire & Surendra Singh Kachhwaha

To cite this article: Suvik Oza, Pravin Kodgire & Surendra Singh Kachhwaha (2022) Analysis
of RSM Based BBD and CCD Techniques Applied for Biodiesel Production from Waste Cotton-
Seed Cooking Oil via Ultrasound Method, Analytical Chemistry Letters, 12:1, 86-101, DOI:
10.1080/22297928.2021.2019611

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Published online: 21 Feb 2022.

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 Anal. Chem. Lett. 12 (1) 2022 pp 86 - 101 86

Article

Analysis of RSM Based BBD and CCD Techniques Applied for

Biodiesel Production from Waste Cotton-Seed Cooking Oil
via Ultrasound Method
Suvik Oza 1,3
, Pravin Kodgire 1,3
* and Surendra Singh Kachhwaha 2,3
1
Chemical Engineering Department, Pandit Deendayal Petroleum University,
Gandhinagar, Gujarat-382007, India
2
Mechanical Engineering Department, Pandit Deendayal Petroleum University,
Gandhinagar, Gujarat-382007, India
3
Center for Biofuel and Bioenergy Studies, Pandit Deendayal Petroleum
University, Gandhinagar, Gujarat-382007, India

* Corresponding Author: pravin.kodgire@sot.pdpu.ac.in (Pravin Kodgire)

Received 01 April 2021; Received in revised form 16 September 2021; Accepted 19 November 2021

Abstract: Biodiesel was produced from the waste cotton-seed cooking oil with methanol in presence of
the calcium oxide catalyst by the ultrasound-assisted transesterification method. The ultrasonication approach
was used for biodiesel production as it significantly lower reaction time and is highly energy- efficient. This
paper-work focused on the optimization of biodiesel production parameters methanol: oil molar ratio (A), CaO
amount (B), process temperature (C) using the two different response surface methodology (RSM) such as
box-behnken design and central composite design (CCD). Also a comparison of the results of the box-behnken
design (BBD) and central composite design (CCD) has been carried out. Quadratic polynomial equations
are obtained by investigating the experimental yield of the transesterification process. The impact of process
parameters on biodiesel yield is discussed by various plots. It was found that the foremost influential parameter
on biodiesel production was the CaO amount based on both BBD and CCD methods. A critical relationship
with experimental results in BBD method R2 value is 97.73%, while within the case of the CCD method R2
value is 99.90%. The Optimized process parameters for the CaO catalyst were determined as Methanol: oil
molar ratio: 12:1; CaO amount (w/w)%: 1%; reaction temperature: 50°C; and the corresponding yield: 96.45%
for BBD and CCD methods, respectively.
Keywords: Biodiesel, Ultrasound system, BBD, CCD, Optimization.
Introduction are ceaselessly draining and non-sustainable.
The worldwide energy frameworks are profoundly Energy and fuel play a virtual role, especially in
subject to petroleum-based products. With rapid the transportation sector 2. The normal utilization
industrial and cosmopolitan development, the of energy in the transportation sector is raised by
absolute global energy utilization is anticipated 1.1% each year, and just this area will represent
to enhance by 28% by the year 2040 1. Today, the 63% of the addition of absolute world liquid fuel
most predominant assets for worldwide energy use from 2021 to 2040 3. The progress of this
requirements are coal, combustible gases, and sector has increased the release of toxins such as
unrefined petroleum. These regular fuel sources hydrocarbon, nitrogen oxides, carbon monoxides,
Anal. Chem. Lett. 2022, 12, 86-101 © 2022 Har Krishan Bhalla & Sons
DOI: 10.1080/22297928.2021.2019611
 Suvik Oza et al. / Anal. Chem. Lett. 12 (1) 2022 pp 86 - 101
and carbon dioxides, which is affecting the air
quality and causing global warming as well as
climate changes. In this way, the scientists have
centered on the issues to discover a substitute
alternative source. For this, biodiesel helps
in insurance of the climate because of its non-
harmful, sustainable, bio-degradable nature as it
produces negligible sulfur emissions and ozone-
exhausting substances. Biodiesel is simple to
utilize in comparison to when obtained from fuel
diesel 1,4,5.
Biodiesel is produced using renewable natural
plant-derivative like vegetable oils which are
either: edible and/or non-edible oils; animal flabs;
algae, as well as waste vegetable oil from houses
and restaurants 1,6. Biodiesel produced by the
transesterification of triglycerides contains ~10%
of built-in oxygen fraction that supports complete
combustion. The appropriate choice of feedstock
for biodiesel production is one of the critical
factors for waning the cost of production 5,7. For
biodiesel production, the main aspect is to have
best, easily available, and low-cost raw material.
The second-generation non edible oil feedstock
have resolved the problems associated with
the first-generation biodiesel feedstock. Since
the biodiesel produced from edible oil will
create a food security problem. Also, the second-
generation biodiesel product from non-edible
oil plant sources are not suitable for human
consumption 1,8.
Currently, every month around 850 crore
liter diesel is consumed in India. As per policy
the government aims to blend 5 percent of
biodiesel in petro-diesel by 2030 9. Thus, 500
crore liters of biodiesel will be required every
year. Being a feedstock with great accessibility,
for India based on estimates waste/used cooking
oil (WCO/UCO) can be seen as a conservative
and cost-effective option. The worldwide UCO
market size was esteemed at $ 6,041.2 million
(42,288.4 crores in India) for the year 2018 10.
India consumed around 1.4 million metric tons
of cottonseed oil in year 2019. Cottonseed oil is
widely utilized for cooking, deep frying, baking
processes in processed food industries as use of
this oil able to extend shelf life of processed food.
Cottonseed oil has higher saturated fat content
87
than other edible oils. This polyunsaturated fat
helps lowering bad cholesterol and increases
good cholesterol 11. Gossypol a toxin found in the
raw cottonseed oil must be removed as it causes
health damages upon human consumption.
Further, it is well known that total polar
compounds (TPC) produced during continuous
frying process due to reaction between peroxides
and hydroperoxides with triglycerides, ketones,
aldehydes makes the leftover oil unhealthy and
considered as waste oil 12. According to the
Food Safety and Standards Authority of India
(FSSAI), if maximum of 1% of total polar
compounds (TPC) are available in the oil, that
oil is considered as the waste cooking oil due to
its harmful nature to human health.
In India, 2700 crore liters of various cooking
oils are used, out of which 140 crore liter WCO
can be collected from the bulk consumer such as
hotels, restaurants, canteens and food business
operators for conversion, which will produce
around 110 crore liters of biodiesel every year
13
. Production of biodiesel from UCO may save
21% of fossil energy as compared with unrefined
petroleum and hoards 96% of energy compared
with petrodiesel manufacture 14.
Process intensification (PI) based biodiesel
production various processes available are
viz., membrane reactor, reactive distillation,
hydrodynamic cavitation, ultrasonic cavitation,
microwave irradiation and, associated and
sequential application of the US and microwave
irradiation 5,15,16. Amongst them, ultra-sonication
is an amazing process of interest. The US
manages the beneficial outcome of ultra-
sonication, which includes the production,
development, and implosive breakdown of
bubbles produced due to constant development
and recompression of pressure in a fluid medium.
During biodiesel production, US irradiation
causes delivering the enormous number of micro-
bubbles close to the phase boundary between the
methanol and triglyceride phase. A few bubbles
remain steady following the above cycle while
others get exposed to the brutal breakdown after
growing to specific bubble size, ensuring better
mass transfer across phases and forming an
emulsion. Enormous energy is conveyed upon the
 Suvik Oza et al. / Anal. Chem. Lett. 12 (1) 2022 pp 86 - 101
incredibly unbalanced breakdown of cavitation
bubbles that ascent under ranges of 20-40 kHz
2,5,7,16
. In such emulsions, at the interfacial area
and mass exchange among the alcohol and oil
phase increases. The homogeneous movement of
reactants moves the equilibrium in a forward way
via simultaneously giving physical and chemical
influences in the transesterification.
Further, the US gives physical blending to
boost activation energy needed to initiate trans-
esterification which enhances the reaction
rate. The use of heterogeneous catalysts is
advantageous due to high yield, ease of recovery
and, reusability and makes a cost-effective
green process. Such catalysts tolerate high
FFA and moisture content 17. CaO catalyst is a
heterogeneous catalyst. CaO catalyst is favored
because of the nominal cost and readily available.
It is easy to recover and, reusability makes a cost-
effective choice for a green process. Calcium
oxide (CaO), a solid base catalyst, is upheld as
an eco-obliging material that advances the long
catalyst life, high activity, and moderate reaction
conditions 5,18. The heterogeneous catalyst is
separate from products by simple-filtration or
centrifugation process 13.
For optimization of the process, researchers
used various methods i.e. response surface
methodology (RSM), artificial neural network
(ANN), extreme learning machine (ELM),
however, the most used method is RSM.
The RSM method includes the techniques
viz. box-behnken design (BBD) and central
composite design (CCD) which are widely
used for optimization. The analysis of variance
(ANOVA) is commonly adopted to develop
the mathematical model through the RSM
techniques such as the BBD and CCD. ANOVA
is a statistical technique which is utilized to
examine the impact of various components/
terms (liner impact (xi)/quadratic (xi2)/interaction
impact (xixj) terms) existing in the mathematical
model 19,20. The F-test in hypothesis testing can be
used the significance of each term. For the most
part, 95% of the certainty stretch is chosen and
might differ depending on the exactness needed
in the forecast utilizing the mathematical model.
Many researchers have utilized the RSM method
88
and ANOVA to the results to carry examination.
Ultrasound is an established process
intensification method used for biodiesel
production as it requires a reduced amount of
energy, smaller process time, tranquil separation
of products, along with a better yield of the
product. The foremost objective of this research
study is to present a reasonable analysis of
applied RSM optimization methods such as box-
behnken design (BBD) and central composite
design (CCD) method for US-supported
biodiesel production dependent on statistical
parameters. The assessment of these methods
based on statistical parameters provides detail
understanding as well as assists the process
designer to select the comparatively cost-
effective and energy-efficient scheme among
available ones that requires less number of
experimental runs to achieve optimum process
conditions for maximizing the biodiesel yield.
Materials and methods
Raw materials
Waste cottonseed cooking oil (WCCO) is taken
from neighborhood restaurants in Ahmedabad,
Gujarat. Prior to use in experimentation, this
oil was filtered to remove the suspended food
particles. Methyl alcohol (99% pure, A.R. grade)
and CaO (purity 99%, A.R. grade) were bought
from M/s Fisher Scientific, India.
Characterization of WCCO and produced
biodiesel
Characterization of WCCO acid profile done by
using the gas chromatography-mass spectroscopy
(GC-MS). The Karl Fischer Titrator was used for
measuring the moisture content. An acid value
and FFA content were determined using an auto
titrator.
The following various instruments were used
for determination of the various physicochemical
properties of the WCCO biodiesel. A bomb
calorimeter (ASTM D4868 method) was used
to determine the calorific value. According to
ASTM (D93), flash point was measured using
closed cup Pensky-Martens. Kinematic viscosity
(at 40oC) as per ASTM (D445) method was
measured using a Brookfield viscometer. Cloud
 Suvik Oza et al. / Anal. Chem. Lett. 12 (1) 2022 pp 86 - 101
point and pour point (ASTM D2500 method)
were measured using the Cloud point and Pour
point equipment. A digital density meter (ASTM
D792 method) was used for determining the
density.
Design of experiment (DOE)
A typical stoichiometric reaction between
triglyceride (TG) and methyl alcohol is shown
below and as per that 1 mol of TG reacts with
3 moles of methanol to produce the 3 moles of
biodiesel and 1 moles of glycerol.
However, the reaction is a second order
reversible reaction and in order to maintain the
forward rate of reaction molar ratio is generally
kept more than 3 (alcohol):1 (oil) (one of the
co-reactant (preferably methanol) is kept at
higher proportion). As mentioned based on the
batch size of oil used for experiments, literature
review as well as performed preliminary
experimentation authors concluded to keep the
molar ratio between 6:1-12:1.
Table 1 shows the ranges of process variables
for biodiesel production. The determined
optimum conditions falls within the selected
ranges close to mid-level. Biodiesel production
from WCCO using CaO catalyzed condition was
optimized using response surface methodology
(RSM) methods. Table 1 provides the process
parameters (independent variables) and the range
of level for experimentation. RSM based BBD
and CCD were used for studying the effects of
process parameters on biodiesel yield. CCD has
the superb estimate capability and is insensitive
Table 1. Independent variables and range of levels used for experimentation
Process variables
Actual Factors
Methyl alcohol/oil molar ratio; (A)
CaO wt %; (B)
Temperature, °C (C)
89
to the absent data as it is robust and covers more
number of level blends than BBD. BBD provide
robust coefficient estimates at the center points
but fails for the predictions at the corner points
as method has no strategy points at corners.
However, a number of experiments for the BBD
are significantly lower as compared to CCD. In
the BBD approach total of fifteen exponential
runs were created, while in the CCD method a
total of twenty experimental runs were created.
A steady reaction time of 10 min and a range of
three levels were chosen based on preliminary
performed experimentation.
Ultrasound-assisted transesterification reaction
Programmable sonicator set up model no: VCX
500; M/s sonic vibracell, USA was utilized for
the biodiesel production. Sonicator can vary
power up to 500 W (amplitude range of 20-100%;
for experimental runs 50% amplitude used)
with a fixed frequency of 20 kHz. Three necks
borosil rector (250 ml capacity) was utilized as
a reaction vessel with a 50 ml oil reactant. It
was observed, that after completion of reaction,
reaction mixture gets separated into two layers.
The top layer comprises unsaturated FAME
with a trance of unconverted oil and a lower
thick brown-colored thick layer is of glycerol.
Three-time washing of biodiesel with DI water
was done to remove trances of KOH and dried to
eliminate trances of dampness.
Response surface methodology (RSM)
Response surface methodology (RSM) is a
collection of statistical mathematical methods
beneficial for evolving, refining, and optimizing
processes. The objective of the watchful design
of experimentation is to enhance a response
that is influenced by numerous self-governing
Levels for variables
-1 0 1
6 12 18
0.5 1 1.5
40 50 60
 Suvik Oza et al. / Anal. Chem. Lett. 12 (1) 2022 pp 86 - 101
parameters. Based on the controlled value of
independent variables the output is obtained
from a well-designed regression analysis 21,22.
The design of the experiment (DoE) and response
surface methodology (RSM) are broadly utilized
in the optimization of the biodiesel production
process. DoE technique is valuable for acquiring
the most extreme data from a negligible number of
all-around arranged investigations by shifting at
the same time all the cycle factor, while the RSM
is an assortment of numerical and measurable
apparatuses for building an experimental model
associating result with the powerful process
factors 5.
RSM has two models based on linearity or
polynomial behavior that is a first-order model
and the second-order model. The regression
analysis was performed on the experimental yield
data to assess the response of biodiesel yield as
y function (refer eq. 1) fitted for a quadratic
polynomial equation, given by:
(1)
Where y is the predicted response value, Bi and
Bij are regression coefficients obtained and can
represent the linear, second-order, and interaction
effect of x1, x2, and x3 …, while n is the number
of independent variables and ε is the random
error 5,19.
BBD and CCD are the types of design of
RSM. BBD uses fewer design points than
central composite designs, therefore makes it an
expensive method to run with the same number of
factors. The BBD has treatment combinations at
the mid-level of the edge of the experiment space
and requires at least three continuous factors.
The BBD also ensures that all factors are not set
to their high levels at the same time 5. BBD has
less number of experiments compared to CCD.
For the development of BBD, the number of
experiments (N) is obtained by expression N =
2n (n-1) + m; where n indicated the number of
experiments and m denotes the number of center
points. Here, both ‘n’ and ‘m’ has a value of 3.
This makes BBD have 15 experimental runs for
3 levels and 3 factors as shown in Table 2.
In the central composite design arrays, the
90
levels of the factors are on the edges, center
and circumscribed at the center of side. CCD
technique is a full or partial factorial design
method with the center point which is amplified
with a gathering of the axial point that grants
evaluation of the non-linearity in the predicted
model 23. For the developments of CCD, the
number of the experiment (N) is found by N = 2n
+ 2n + m, where n is the number of independent
variables and m is the number of replicated
central point. For the current system, n = 3 and
m = 6. This form set of 8 cube points, 6 axial
points, and 6 repeated center data; and totaling
20 experiments runs (refer table 2) which were
analyzed in a randomized order where axial
point, α =1.682.
Using design-expert® software (edition 11,
stat-Ease Inc., USA), experimental yield data of
both BBD (15 experimental runs) and CCD (20
experimental runs) were used as input to examine
optimized biodiesel. ANOVA was carried out
on the experiment yield values to determine
the coefficient of the second-order polynomial
model. ANOVA results give a relationship among
the variations caused by experimental values and
assert suitability of the predicted model. This is
verified by analyzing the values of terms the sum
of the square root (SS), the mean square (MS),
p-value, the Fischer test (F-test), and the ‘lack of
fit’ test (LOF). The evolution of the model is done
by the coefficient of determination (R2) and the
accuracy of the obtained quadratic polynomial
model was also evaluated. The model is whether
significance or not was checked by F-test.
Result and Discussion
Characterization of WCCO feedstock
Characterization of WCCO was done by using
gas chromatography-mass spectroscopy (GC-
MS). Various fatty acid contained of the WCCO
was analyzed by the gas chromatography-
mass spectroscopy. GCMS analysis showed
that saturated palmitic acid (C16H32O2; C16:0),
monounsaturated oleic acid (C18H34O2; C18:1) and
polyunsaturated linoleic acid (C18H32O2; C18:2)
were the major fatty acid components present in
the waste cooking oil. The complete fatty acid
profile consists of: 8.5% of palmitic acid; 3.1% of
 Suvik Oza et al. / Anal. Chem. Lett. 12 (1) 2022 pp 86 - 101 91

Table 2. List of observations considered in DOE for BBD

and CCD models. (Bold term is maximum yield value)

Run Order Methyl alcohol CaO wt% Temperature Experimental Predicted yield
: oil molar (B) °C (C) Yield % %
BBD CCD ratio (A) BBD CCD BBD CCD
1 - 6.00 1.00 60.00 88.10 - 88.12 -
2 - 18.00 0.50 50.00 78.34 - 79.16 -
3 - 6.00 1.50 50.00 81.50 - 80.66 -
4 - 18.00 1.00 60.00 85.89 - 83.88 -
5 - 12.00 0.50 40.00 87.00 - 86.19 -
6 - 12.00 1.50 60.00 81.23 - 82.03 -
7 - 18.00 1.00 40.00 85.60 - 85.56 -
8 - 6.00 1.00 40.00 87.54 - 89.54 -
9 1 12.00 1.00 50.00 94.00 94.00 95.25 95.25
10 2 12.00 1.00 50.00 95.32 95.32 95.25 95.25
11 - 12.00 1.50 40.00 75.59 - 74.42 -
12 - 18.00 1.50 50.00 70.21 - 71.40 -
13 3 12.00 1.00 50.00 96.45 96.45 95.25 95.25
14 - 6.00 0.50 50.00 79.32 - 78.12 -
15 - 12.00 0.50 60.00 74.32 - 75.48 -
- 4 12.00 1.84 50.00 - 57.47 - 57.47
- 5 12.00 0.16 50.00 - 61.86 - 61.86
- 6 6.00 1.50 60.00 - 81.39 - 81.39
- 7 18.00 0.50 40.00 - 81.45 - 81.45
- 8 6.00 1.50 40.00 - 73.65 - 73.65
- 9 1.91 1.00 50.00 - 83.62 - 83.62
- 10 22.09 1.00 50.00 - 76.71 - 76.71
- 11 6.00 0.50 60.00 - 69.69 - 69.69
- 12 18.00 0.50 60.00 - 70.60 - 70.60
- 13 18.00 1.50 40.00 - 64.52 - 64.52
- 14 12.00 1.00 50.00 - 95.25 - 95.25
- 15 12.00 1.00 50.00 - 95.25 - 95.25
- 16 12.00 1.00 66.82 - 85.06 - 85.06
- 17 12.00 1.00 33.18 - 87.67 - 87.67
- 18 18.00 1.50 60.00 - 71.99 - 71.99
- 19 6.00 0.50 40.00 - 80.27 - 80.27
- 20 12.00 1.00 50.00 - 95.25 - 95.25

stearic acid; 21.2% of oleic acid; 55.2% of linoleic acid value should be < 2.1 mgKOH/g and moisture
acid and 5.9% of linolinic acid. Moisture content, content less than 0.5% of the WCCO for biodiesel
acid value and fatty acid are the main parameters production. Here WCCO used found to have acid
analyzed for WCCO prior the experiments. The value of 1.2 mgKOH/g and moisture contents
 Suvik Oza et al. / Anal. Chem. Lett. 12 (1) 2022 pp 86 - 101
of 0.3% for biodiesel production. The kinematic
viscosity (at 40°C) has found of 52.04 mm2/s for
biodiesel production.
RSM statistical analysis
The statistical optimization of the process
parameters was performed using the design-
expert software (edition 11; Stat-Ease, Inc.,
USA) to maximize the biodiesel yield as per
the process mentioned in section “Ultrasound-
assisted transesterification reaction”. The results
of regression and analysis of variance (ANOVA)
of biodiesel yield were dissected by selecting the
best possible model either linear or quadratic.
Second-order quadratic regression model
was obtained to be the best fit for both RSM
methods. As mentioned earlier for three factors,
experiments sets were generated of fifteen
factorial points in the BBD model and twenty
factorial points in the CCD method (Table 2). The
two techniques utilized the regression condition
regarding uncoded factors created through the
curve fitting utilizing the least square method
through generated the predicated regression
equation mentioned below,
The regression equation for the BBD method
y = -9.519 + 4.129A + 62.544B +
2.161C-0.859AB-0.001AC + 0.916BC-0.148A2-
50.323B2-0.031C2 (2)
The regression equation for the CCD method
y = -9.558 + 4.129A + 62.555B +
2.162C-0.859AB-0.001AC + 0.916 BC-0.142A2-
50.329B2-0.031C2 (3)
Where, A, B, and C are the encoded forms of
methyl alcohol: oil molar ratio, CaO amounts,
and reaction temperature correspondingly. In
both methods of BBD and CCD, over-all nine
terms are generated in regression equation (Eq.
2 and Eq. 3), out of them, three terms of liner
term A, B, C represents main effects, next three
terms AB, BC, AC are represented interaction
effects, and remaining three terms A2, B2, C2
are represented quadratic effects of the factors.
The maximum experimental yield was obtained
corresponding to 96.45% (Table 2) in the BBD
and CCD respectively. Table 3 (A and B) shows
the detailed ANOVA of parameters for BBD and
CCD methods.
92
Based on Table 3 (a and b), the values of
F-value terms for both methods of BBD and
CCD were obtained 23.920 and 1059.860
respectively. The p-value is found to be less
than 0.05 for both methods, so it’s showed that
the model is significant. The values of p-value
terms for both the model are obtained 0.001 and
<0.0001 respectively. The ‘lack of fit’ F-values
for the BBD and CCD are founded 3.610 (Table
3 (A)) and 1.4E-7 (refer table 3 (B)) respectively,
moreover the P-value for both model are greater
than 0.05 also it’s justified that the lack of fit
terms is no significant for this experiment.
The higher value of the coefficient of
determination (R2) indicates the accuracy and
developed the model is the best fit with the
predicted model data and additional, terms
adjusted coefficient of determination (Adj. R2)
was assessed which indicates the model fitness 5.
For the Box-Behnken design model, the R2 and
Adj. R2 values were obtained 0.9773 and 0.9365
respectively also both term's differences are less
than 0.4. When, in the CCD model, the R2 and
Adj.R2 values were obtained 0.999 and 0.998
respectively and both terms between differences
in very less.
As per the analysis of the developed quadratic
model, as seen in Table 3 (a) the significant model
terms found in the BBD model were A, AB, BC,
A2, B2, C2 and remaining terms are insignificant.
While, Table 3 (b) indicates that terms A, B,
C, AB, BC, A2, B2, C2 are the significant and
interaction term of AC is insignificant in CCD
based model. The R2 value is higher in the CCD
model compare to the BBD model.
In the BBD and CCD model, the biodiesel
yield data are regularly dissipated along the
straight line of 45° that showed up in Fig. 1 (a
and e). The predicted yield values were dispersed
reliably close to the real response and this verifies
that developed regression models is best fit the
connection between the process variables and
biodiesel yield. Fig. 1 (b and f) shows the plots of
the normal percentage probability vs. residual data
of biodiesel yield for the BBD and CCD model,
respectively. It shows a respectable connection
between externally studentized residuals and
their normal percentage probability rank position
Table 3. Result of the ANOVA for the biodiesel production using (a) BBD & (b) CCD method. (Bold terms are significant)

a. Box-Behnken Design (BBD) b. Central Composite Design (CCD)

Source dof. Sum of squares Mean Square F- value p-value dof. Sum of squares Mean Square F- value p-value
Model 9 830.770 92.310 23.920 0.001 9 2868.630 318.740 1059.860 < 0.0001
A 1 33.700 33.700 8.730 0.032 1 57.630 57.630 191.640 < 0.0001
B 1 13.650 13.650 3.540 0.119 1 23.300 23.300 77.480 < 0.0001
C 1 4.790 4.790 1.240 0.316 1 8.220 8.220 27.350 0.0004
AB 1 26.570 26.570 6.890 0.047 1 53.150 53.150 176.730 < 0.0001
AC 1 0.018 0.018 0.005 0.948 1 0.037 0.037 0.122 0.7338
BC 1 83.910 83.910 21.740 0.006 1 167.810 167.810 558.010 < 0.0001
A2 1 105.030 105.030 27.220 0.003 1 410.130 410.130 1363.760 < 0.0001
B2 1 584.410 584.410 151.450 < 0.0001 1 2281.470 2281.470 7586.340 < 0.0001
C2 1 36.420 36.420 9.440 0.028 1 142.290 142.290 473.150 < 0.0001
Residual 5 19.290 3.860 10 3.010 0.301
Lack of Fit 3 16.290 5.430 3.610 0.224 5 4.38E-07 8.76E-08 1.46E-07 1
Pure Error 2 3.010 1.500 5 3.010 0.602
Total 14 850.060 19 2871.630
2 2
R = 0.9773; Adj. R =0.9365 R2= 0.999; Adj. R2=0.998
Suvik Oza et al. / Anal. Chem. Lett. 12 (1) 2022 pp 86 - 101
93
 Suvik Oza et al. / Anal. Chem. Lett. 12 (1) 2022 pp 86 - 101
data. In this CCD model graph, mostly all the
data points are arranged in straight line due to the
externally studentized residual data are almost
zero (i. e. error is 0.04). Fig. 1 (c and g) shows the
response plots of externally studentized residuals
versus plotted against the predicted data of yield
for BBD and CCD model, respectively. In this
plot, all the data points are randomly scatted to
the reference line. It generally indicates that the
regression model shows amazing adequacy of
the biodiesel process. Fig. 1 (d and h) shows the
pareto chart of the standardized effect vs. various
terms for BBD and CCD model, respectively. In
this BBD model graph, the quadric terms B2 is
high effect on the response (biodiesel), while
liner terms of B & C and interaction term AC
are insignificant (Fig. 1(d)). In this CCD model
graph, the quadric terms B2 is high effect on the
response (biodiesel), while interaction term AC
is insignificant (Fig. 1(d)).
Main effects and interaction effects
Fig. 2 (a and b) of the perturbation plots of
process variables affecting biodiesel yield
for both BBD and CCD method. Perturbation
graphs aids in understanding the affectability
of individual factor and their variations while
keeping the excess elements consistent 5,20. In
the BBD model, (Fig. 2(a)) process parameter
of B is increase in biodiesel conversion with an
increase process parameter of A up to middle
level values of 1:1, however, again increase in B
above the higher level values of 1.5:1 decreases
biodiesel conversion. While in the CCD the
parameter of catalyst amount (B) represents
the same as in the BBD model in the parameter
of catalyst amount (B) is increase in biodiesel
conversion with an increase process parameter
of A up to middle level values of 1:1, however,
again increase in B above the higher level
values of 1.5:1 decreases biodiesel conversion.
The nature of the factor which has a more
inclined slope when contrasted with planner
one indicates that it affects the biodiesel yield
significantly. In the BBD model, (Fig. 2(a))
process parameter B has the perturbation effect
influence (exhibiting steep slope) between lower
level (-1) to intermediary level (0) followed by
94
the process variables A and C. When, in the CCD
model (Fig. 2(b)), process parameter B has the
perturbation effect influence (exhibiting steep
slope) between lower level (-1) to intermediary
level (0) followed by the process variables A
and C.
The analysis of the effect of singular process
variable on WCCO- biodiesel yield offers detailed
understanding however is incapable to give an
all-encompassing perspective concerning the
variation in yield. To discover the impact among
demonstrated variables, 3-D surfaces along with
a 2-D contour plot need to be inspected.
Fig. 3(a) exhibits an interaction plot of WCCO-
biodiesel yield for molar ratio and CaO wt% for
BBD (@ keeping the temperature constant at the
intermediate level). The elliptical shape of the
yield profile represented the interaction between
the process parameters of molar ratio and CaO
wt%. The greater than 90% yield was obtained
for a CaO wt% in the range of 0.88%-1.08% and
molar ratio in the range of 9.06-12.8 at a constant
temperature of 50°C. The rest of the profile of
graph represented the yield profiles decay
consistently in degree towards outward heading.
Fig. 3(d) exhibits an interaction plot of WCCO-
biodiesel yield with respect to molar ratio and
CaO wt% for CCD (@ keeping temperature
constant at the intermediate level). The grater
than 90% yield was existed for the CaO wt% in
the range of 0.88%-1.09% and molar ratio in the
range of 9.0-12.71 at a constant temperature of
50°C.
Fig. 3(b) exhibits the interaction effect of
reaction temperature and molar ratio for BBD
(catalyst amount kept constant at the intermediate
level). Yield profile region higher than 95%,
exists for a molar ratio in the range of 9.0-12.71
and temperature in the range of 44.78°C-52.78°C.
Fig. 3(e) exhibits the interaction effect of reaction
temperature and molar ratio for CCD (@ catalyst
amount kept constant at the intermediate level).
Yield profile region higher than 95%, exists
for a molar ratio in the range of 9.0-12.70 and
temperature in the range of 44.80°C-52.78°C.
Fig. 3(c) shows the interaction effect of
reaction temperature and CaO wt% for BBD
(@ molar ratio kept constant at the intermediate
 Suvik Oza et al. / Anal. Chem. Lett. 12 (1) 2022 pp 86 - 101 95

Figure 1. (a and e) Comparison of actual and predicted conversion (%); (b and f)

Normal probability plot of residuals; (c and g) Externally studentized residuals
for both model of BBD and CCD respectively
 Suvik Oza et al. / Anal. Chem. Lett. 12 (1) 2022 pp 86 - 101 96

Figure 1 cont. (d and h) Pareto chart of the standardized

effects for both model of BBD and CCD respectively

Figure 2. Perturbation plots for process variables for (a) BBD and (b) CCD method
level). The realistic region for higher yield (≥
90%) is 0.61%-1.31% range of the CaO wt%
and temperature in the range of 40°C-60°C.
Fig. 3(f) shows the interaction effect of reaction
temperature and CaO wt% for CCD (@ molar
ratio kept constant at the intermediate level). The
realistic region for higher yield (≥ 90) is 0.60-
1.30 range of the CaO wt% and temperature
in the range of 40°C-60°C. It was found that
biodiesel yield increases with the increase in the
operating factors until a specific value beyond
which the biodiesel yield declined. The decline
in biodiesel yield was because of the reversible
response of the transesterification reaction.
Optimization of the process parameters
The RSM mathematical optimization procedure
was used for investigating the ideal response
conditions within the scope of the control factors
by contemplating the standard blunder (StdErr)
that occurred in the model. Fig. 4 shows that
the lower and upper limits of the range for all
the parameters are included in this optimization
process 1. As indicated by the breaking point
basis for biodiesel yield optimization, the
second order polynomial equation, i.e., Eq. (2)
and (3) were applied to optimize the operating
process conditions by utilizing mathematical
RSM optimization in BBD and CCD
 Suvik Oza et al. / Anal. Chem. Lett. 12 (1) 2022 pp 86 - 101 97

Figure 3. 3-D surface plot and Contour plot of interaction effect [(a) and (d)] methanol/oil molar
ratio and CaO wt%; [(b) and (e)] methanol/oil molar ratio and temperature; [(c) and (f)]
CaO wt% and temperature; on biodiesel yield for both models of BBD and CCD

approaches. By utilizing the Design-Expert Comparison of RSM method of BBD and

software, various arrangements of various
optimal operating factors and corresponding
biodiesel yields are created. In the BBD model,
the optimal solution of parameters found to be
10.945, 0.967, and 48.31°C respectively for
molar ratio (A), CaO wt% (B), temperature
(C), and also at this optimal condition, the
predicted yield is 95.544% (experimental yield
96.45%) as shown in Fig. 4 (a). For this optimal
condition, the desirability got values of 0.850
which is nearest to the 1. In the CCD model,
the optimal solution of parameters is 10.945,
0.968, and 48.31°C respectively for molar ratio
(A), CaO wt% (B), temperature (C) and also
at this optimal condition, the predicted yield
is 95.541% (experimental yield 96.45%) as
shown in Fig. 4 (b). For this optimal condition,
the desirability got values of 0.895 which is
nearest to the 1.
CCD approach
In this study, both analytical tools of RSM
i.e. BBD, and CCD approaches have given
outstanding outputs for optimization of
process variables of transesterification process.
Examination of the outcome indicated that
the results obtained from both models of BBD
and CCD of RSM statistical procedures were
in agreement with one another. However, the
sequence of the important parameters is not
the same in both approaches. In the BBD, the
liner terms of B & C and interaction terms of
AC are insignificant, while in the CCD, only
one interaction term AC is insignificant. The R2
value is higher in the CCD (0.999) compare to
the BBD (0.9773). It means that a high number
of experiments number of sets are given around
the accurate result. In the BBD, the experiment
number of the set is fifteen while, in CCD twenty
 Suvik Oza et al. / Anal. Chem. Lett. 12 (1) 2022 pp 86 - 101
Figure 4. The optimal reaction condition for (a) BBD and (b) CCD models
number of the set of experiment. Hence, it is
prescribed to utilize RSM (CCD) to produce
exact enhancement conditions in light of the
fact that the necessity of bigger exploratory
information in RSM gives low normal error
towards modeling and experimental validation.
In the predicted vs. actual graph of the CCD
method in all the data point very closely the
reference line to compare the BBD method plot.
In the 3-D surface plots and Contour plots of
interaction effects of biodiesel, the yield was
obtained the nearly close outcomes in the both
methods of BBD, and CCD. The desirability
value of 1 is indicated the optimal of the process
gives accurate outcomes in the process. So,
that here, the desirability values are obtained
the 0.850 for the BBD method, 0.895 for the
CCD method. Its means that a high number of
experiments number of sets are given around the
accurate result. In the BBD, the number of the
98
experiment of the set are fifteen while, in CCD
twenty are experiments number of sets present.
RSM has indicated the quantifiable centrality of
all potential blends of interaction and quadratic
terms parameters dependent on a 95% certainty
interval and this can help with perceiving the
future course of an ideal reaction. Furthermore,
the alluring work in RSM can without a very
remarkable stretch choose the ideal operating
process condition inside the extent of levels of
components.
Physicochemical properties of the WCCO-
biodiesel
Table 4 shows the measured physicochemical
properties of biodiesel in the current study and
its comparison with the ASTM standards. The
kinematic viscosity of 3.76 mm2/s and density of
880 kg/m3 are obtained. These values are in the
range of the ASTM standard of the biodiesel.
 Suvik Oza et al. / Anal. Chem. Lett. 12 (1) 2022 pp 86 - 101 99

Table 4. Physicochemical properties of WCCO-biodiesel along with ASTM standard

Property Biodiesel (ASTM) Biodiesel (Present Study)

Acid value (mg KOH/g) Max. 0.50 0.3
Calorific value (MJ/kg) 38 39.3
Kinematic viscosity at 40°C (mm2/s) 1.9 to 6.0 3.76
Flash point (°C) 100 to 170 152
Cloud point (°C) -15 to -16 -15
Pour point (°C) -3 to -12 -8
Density at 15°C (kg/m3) 860 to 900 880

The acid value, calorific value is obtained of the
0.3 mg KOH/g and 39.3 MJ/kg. They are closely
matched with the standard value of biodiesel.
The value of the flash point obtained 152°C. This
value in-between the range of 100°C to 170°C of
a stander value of flashpoint of biodiesel. High
value risk down the fire hazard of fuel when
contacted with ignition sources. The cloud and
pour point values of -15°C and -8°C have been
observed for the biodiesel indicates it can be
easily used in cold climate. All the properties
values of the WCCO-biodiesel are obtained in
the range of the ASTM biodiesel values.
Conclusion
In this work, the process parameters were
optimized utilizing box-behnken design (BBD)
and central composite design (CCD) approach of
the RSM technique. Both BBD and CCD agreed
that catalyst amount to be the most influencing
factor in the biodiesel production from WCCO
catalyzed by CaO. Both methods provide a good
prediction of the biodiesel yield in terms of molar
ratio, CaO wt%, and temperature. A critical
relationship with experimental results in BBD
method R2 value is 97.73%, while within the
case of the CCD method R2 value is 99.90%. The
optimized process parameters for the CaO catalyst
were determined as methyl alcohol: oil molar
ratio: 12:1; CaO wt%: 1%; reaction temperature:
50°C; and the corresponding yield: 96.45% for
BBD and CCD methods, respectively. These two
techniques have given a decent expectation of the
biodiesel yield with respect to molar ratio, CaO
wt%, and temperature. According to this study,
the CCD has higher R2 values to compare the
other method of BBD, and also CCD given the
better outcomes of the other optimal parameters
to compare the outcomes of the parameters of
the BBD method. Physicochemical properties of
produced biodiesel were found to be within the
prescribed ASTM standards and biodiesel can be
used for blending with petro-diesel.
Acknowledgement
The authors desire to recognize Gujarat Energy
Development Agency (GEDA), Gujarat, India,
for supporting this research work and the Centre
for Biofuels and Bioenergy Studies (CBBS) in
PDPU for providing laboratory facilities for this
project.
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