Energy Sources, Part A: Recovery, Utilization, and

Environmental Effects

ISSN: 1556-7036 (Print) 1556-7230 (Online) Journal homepage: https://www.tandfonline.com/loi/ueso20

Evaluating the predicting capability of response

surface methodology on biodiesel production from
grapeseed bio-oil

Hariram Venkatesan, Bose A & Seralathan Sivamani

To cite this article: Hariram Venkatesan, Bose A & Seralathan Sivamani (2019): Evaluating
the predicting capability of response surface methodology on biodiesel production from
grapeseed bio-oil, Energy Sources, Part A: Recovery, Utilization, and Environmental Effects, DOI:
10.1080/15567036.2019.1649759

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ENERGY SOURCES, PART A: RECOVERY, UTILIZATION, AND ENVIRONMENTAL EFFECTS
https://doi.org/10.1080/15567036.2019.1649759

Evaluating the predicting capability of response surface

methodology on biodiesel production from grapeseed bio-oil
Hariram Venkatesan, Bose A, and Seralathan Sivamani
Department of Mechanical Engineering, Hindustan Institute of Technology & Science, Hindustan University, Chennai,
India

ABSTRACT ARTICLE HISTORY

The present study is focussed to understand the importance and conse- Received 27 May 2019
quence of alternative possibilities of simulating, modeling, and optimizing Revised 12 July 2019
methodologies and of the procedural enhancement in soft computing, Accepted 21 July 2019
particularly, in the process of transesterification to produce biodiesel.
KEYWORDS
Here, grapeseed oil is extracted from its feedstock through a combination Grapeseed biodiesel;
of cold pressing and soxhlet extraction process. Single-stage transesterifica- transesterification; RSM;
tion was employed with catalyst concentration, molar ratio, and reaction molar ratio; catalyst
duration as the process parameters for the transformation of mono-alky concentration
triglycerides to fatty-acid methyl esters. The effectiveness and coherence of
the response surface methodology (RSM) tool in predicting the biodiesel
yield were measured in accordance with central composite designusing the
interdependence ANOVA coefficients. Furthermore, the optimal process
parameters of the transesterification process which produced maximum
grapeseed biodiesel were compared with the outcome of RSM methodol-
ogy to understand its efficacy. The RSM tool predicted the maximum yield
of biodiesel as 97.62% from catalyst concentration of 1.045 g of NaOH,
molar ratio of 0.2758 v/v, and reaction duration of 66.6 min, which was then
validated experimentally with a yield of 97.7% grapeseed biodiesel. The
grapeseed biodiesel thus produced was tested for its physiochemical prop-
erties and was found to be within ASTM standards.

Introduction
The escalated demand and rapid depletion of fossil fuels led to the development of newer
methodologies to generate energy. Nowadays, the world witnesses a large increase in the number
of vehicles and the release of potentialharmful emissions into the earth’s atmosphere. The
dependency on fossil fuels such as petroleum and diesel and environmental pollution can be
leveraged by using biofuels. The energy scenario in the engineering world is mainly focussing on
bio-based fuels such as vegetable oil, micro-macro algal oil, waste cooking oil, etc. Biodiesel from
vegetable-based oil is being touted as one of the favorites among the other sources. Biodiesel can
be produced in many ways such as heating, pyrolysis, thermal cracking, and transesterification,
among which transesterification process remains one of the most preferred and successful
methodologies in the production of biodiesel. Acid-catalyzed transesterification process with
sulphuric acid and base-catalyzed transesterification process with methanol at elevated tempera-
ture successfully break down the long-chain mono-alkyl esters into short-chain fatty acid methyl
esters (FAMEs) with the influence of NaOH as catalyst (Venkatesan et al. 2017b). The nonedible
feedstocks such as pongamia, neem, mahua, linseed, cottonseed, karanja, etc. find themselves in

CONTACT Hariram Venkatesan connect2hariram@gmail.com Department of Mechanical Engineering, Hindustan Institute

of Technology & Science, Hindustan University, Chennai, India.
Color versions of one or more of the figures in the article can be found online at www.tandfonline.com/ueso.
© 2019 Taylor & Francis Group, LLC
2 H. VENKATESAN ET AL.

a better place in their use as a vegetable-based biodiesel. Likewise, grapeseed is one of the
potential sources of biodiesel in the Indian subcontinent. Annually, about 24.7 lacs tonnes of
grape are cultivated in India using 79.6,000 hectares of cultivable land. On an average, 4% by
weight of seeds from grape produces around 1.2 lacs tonnes, which is said to be the potential
bioresourceful feedstock for biodiesel (Jelena et al. 2015, Demirbas 2005).
Despite having numerous advantages such as ecofriendliness, biodegradability, renewable nature,
higher miscibility with petro-diesel, and comparatively high flash and fire point, its use as a vegetable-
based biodiesel faces a significant level of challenges in commerciality, which involves higher capital
cost when compared to petroleum-based fuel. This issue can be overcome bytwo ways. One, by
processing the used oil as transportation fuel which may bring down the source cost considerably
and the other way is by optimizing the biodiesel production process with the help of soft computing
tools such as Krigin model, adaptive neurofuzzy interference system (ANFIS), artificial neural network
(ANN), and response surface methodology (RSM) which can constructively reduce the processing and
production cost of biodiesel. Optimization of biodiesel production process through predicting the
variable parameters of transesterification procedure using soft computing tools such as ANN, ANFIS,
and RSM systems yield better and reliable results; thereby, the processing cost and time duration are
reduced greatly. Using the above methods, the correlations of process production parameters and their
interactions can be assessed and optimized (Kumar and Dinesha. 2018).
Many researchers reported the biodiesel production from raw vegetable oil and optimization
of the operating variables using DoE and soft computing tools. Singh et al. (2018) optimized
the procedural technique for the production of grapeseed biodiesel using Taguchi’s orthogonal
array with catalyst concentration, molar ratio, and reaction duration as the variable factors.
The maximum biodiesel yield along with optimal viscosity was found to be 1% catalyst
concentration, 6:1 molar ratio, and 60 min reaction duration at 60°C reaction temperature.
Gunawan et al. (2014) reported on the production of biodiesel from Xylocarps moluccas seed
oil through continuous transesterification process. 2 ml/g of methanol to oil molar ratio, 0.3%
KOH, 1% sulphuric acid, and 20-min esterification period reduced the saturated fatty acid
content from 22% to 1.2% and further yielded 97% of biodiesel. The authors concluded that
the cold flow properties were enhanced in the derived biodiesel. Fernandez et al. (2010) used
n-hexane solvent and soxhlet apparatus for the extraction of bio-oil from grapeseed which
yielded 18.4% of bio-oil. Further, biodiesel produced through in situ transesterification process
was found to have good oxidative stability and increased cold flow properties. Few other others
(Duz, Saydut, and Ozturk 2011, Gui et al. 2008 and Bankovic-illic, Stamenkovic, and Veljkovic
2012) reported on oil extraction process through soxhlet and solvent extraction method. The
biodiesel was produced through thermal cracking, microemulsion, and microwave-assisted
transesterification process, which yielded better results. Kaya et al. (2009) and Antolin et al.
(2002) used NaOH as a catalyst during the transesterification procedure. NaOH quantity
ranging between 0.34 g and 1.5 g was used in their study. With methanol as the base, the
yield of biodiesel was 89 to 92.47%.
RSM is a vigorous and robust computational tool which finds its application in simulation,
modeling, DoE, and optimization studies. The key advantage of employing RSM is its capability to
curtail the required number of experimental trials for assessing the synergetic effect of output and
input operating parameters. Few researchers successfully established the empirical relationship and
formulated the linear regression statistics to produce vegetable oil-based biodiesel through transes-
terification method. Rashid Anwar et al. (2011) formulated the central composite design (CCD)
using the variable parameters to produce moringa biodiesel ascertained by RSM. 6.4:1 methanol to
oil molar ratio, 55°C reaction temperature, 0.80% catalyst concentration, and 7-min reaction dura-
tion yielded 93.3% of Moringa oleifera Methyl ester (MOME). Betiku et al. (2016) enhanced the
multistage transesterification process using ANN and RSM. They used the Behnken factorial design
for fitting the second-order responses and coupled genetic algorithm with RSM, ANFIS, and ANN
where RSM was ascertained to be superior in process optimization.
 ENERGY SOURCES, PART A: RECOVERY, UTILIZATION, AND ENVIRONMENTAL EFFECTS 3

Eriola Betiku et al. (2018) compared the predicting capability of RSM and ANN to evaluate the
effectiveness of computing models in bio-oil extraction process. A five-level three factorial CCD was
introduced in the extraction process with the function of time. RSM too demonstrated the enhanced
interactive effect between the responses and input parameters. Few researchers and Mostafaei
(2018)) used ANFIS technique to predict the physiochemical properties such as cloud point, pour
point, kinematic viscosity, cetane number, and iodine value in the FAME’s of vegetable-based
biodiesel. Even ANN, ANFIS, and RSM techniques were evaluated comparatively by few authors
in their study (Ameer et al. 2017). However, limited investigations could be seen in optimizing and
predicting the operating variables during the transesterification process for obtained biodiesel. It is
worthy to note that few literature were reported using ANFIS in modeling the emission and
performance phenomena of a direct injection CI engine (Hosoz et al. 2013) and ANN and ANFIS
in sugarcane bagasse delignification process (Valim et al. 2017). Recently, the predicting capabilities
of ANN, ANFIS, and RSM were evaluated in the pretreatment stages of transesterification process to
diminish the free fatty acid content. It concluded that both ANN and RSM were explicit and
canonical and RSM was slightly better than ANFIS.
Therefore, the present study is aimed at understanding the transesterification process and its
optimization methodology using RSM. Here, grapeseed oil is extracted from its feedstock through
a combination of cold pressing and soxhlet extraction process. Single-stage transesterification was
employed with catalyst concentration, molar ratio, and reaction duration as the process parameters
for deriving biodiesel. The effectiveness and coherence of the RSM tool in predicting the biodiesel yield
were measured in accordance with CCD using the interdependence ANOVA coefficients. Furthermore,
the optimal process parameters of the transesterification process which produced maximum grapeseed
biodiesel were compared with the outcome of RSM methodology to understand its efficacy.

Materials and methods

Material source
Grapeseeds were supplied by Noyer overseas India Pvt Ltd, Pune, Maharashtra, India. The moisture
content of the grapeseeds was around 6.79 wt%. The seeds were manually cleaned of dust and stones
before extraction. Seeds were stored in sealed plastic bags at room temperature 27±3°C. n-hexane
and 99% pure laboratory grade methanol along with sodium hydroxide as catalyst were used in this
experiment, which was supplied by Vetri Chemicals (Chennai, Tamil Nadu, India).

Oil extraction
The grapeseeds were dried in the ambient temperature for 3 days before oil extraction. The bio-oil
from grapeseeds was extracted by employing a two-step procedure. In the initial step, the grapeseeds
were subjected to cold pressing which was then followed by Soxhlet extraction process as shown in
Figure 1. Sonar S.A 2009 domestic oil press machine was used to extract oil from the seeds. The
machine had an input capacity of 3–5 kg per hour. The initial extraction of grapeseed oil was about
8% through the cold pressing method. The remains of the cold press were sun-dried for 24 h and
were subjected to Soxhlet extraction process for four cycles in 6 h with hexane as solvent. This
process yielded 7.8% of grapeseed bio-oil, whereas cumulative yield with the combination of both the
extraction process was noticed to be 15.8%. Similar, oil extraction efficiency was also reported by
Fernandez et al. (2010) in their studies.

Transesterification
Bio-oil extracted from grapeseed was subjected to titration process with phenolphthalein to estimate
the FFA content and was found to be 1.47%. The acid value of grapeseed bio-oil was noticed to be
4 H. VENKATESAN ET AL.

1.4 (mg of KOH/g) which indicated single-stage transesterification process as a suitable method to
produce grapeseed bio-diesel. The yield of biodiesel depends on the variable process parameters such
as mixing intensity, reaction time, catalyst concentration, molar ratio, and reaction temperature.
Transesterification process with 100 ml of grapeseed bio-oil, appropriate amount of methanol,
catalyst concentration (in terms of weight of oil), rotational agitation speed of 500–600 rpm, and
reaction temperature of 60°C was carried out. The alcohol and catalyst used in the transesterification
process were methanol and sodium hydroxide, respectively. 100 ml of grapeseed oil was taken in the
flat-bottomed erlenmeyer flask and heated up to 90°C to remove the moisture from the bio-oil. The
bio-oil was cooled down to 60°C during which the reaction process was initiated. Methanol was
thoroughly mixed with sodium hydroxide to form a homogenous amalgamated solution of sodium
methoxide. Sodium methoxide solution was then mixed into the oil and the rotational agitation
speed of 500–600 rpm with the help of magnetic stirrer was maintained at 60°C throughout the
reaction process. The mixture content was transferred into a separation flask at the end of the
reaction and layer separation period of 90 mins was allowed during which ring formation took place
separating the glycerol and biodiesel (Venkatesan et al. 2017a). The obtained biodiesel was heated up
to 100 °C to remove moisture content and remaining methanol. The grapeseed biodiesel acquired is
shown in Figures 1 and 2.

Figure 1. Process flow diagram for extraction and transesterification of grape seed oil

Figure 2. Raw grape seed (A), Oil extraction (B), Extracted bio-oil (C) and Grape seed bio-diesel (D)
 ENERGY SOURCES, PART A: RECOVERY, UTILIZATION, AND ENVIRONMENTAL EFFECTS 5

Experimental design and RSM model development

The biodiesel yield depends mainly on independent parameters such as molar ratio (x1 ), catalyst
concentration (x2 Þ, and reaction duration (x3 ). The change in the variables affects the biodiesel yield
significantly and to reduce the loss of time and energy, there is a need to determine the optimal
usage of catalyst concentration, methanol to oil molar ratio and reaction duration. Therefore, the
RSM approach was adopted toaugment and optimize the process operational variables and to attain
maximum yield of grapeseed bio-diesel. The experimental trials were executed in accordance with
the central composite rotatable design (CCRD) of three-factor five level design and the input
variables were coded to five levels – α, −1, 0, 1, and + α as mentioned in Table 2.
The experiment consisted of six center points, six axial points, and eight factorial points, which
furnish 20 experimental data, and the axial point 1.68 was chosen for orthogonality of the model.
The experimental data from the CCRD were analyzed and fitted into the second-order polynomial
mathematical equation as given in Equation 1.

y ¼ b0 þ b1 x1 þ b2 x2 þ b3 x3 þ b11 x12 þ b22 x22 þ b33 x32 þ b12 x1 x2 þ b1:3 x1 x3 þ b23 x2 x3 (1)
where “y” represented the biodiesel yield; b1,b2, and b3 were linear coefficients; b11,b22, and b33 were
quadratic coefficients; b12,b13, and b23 were interactive coefficients; and x1 , x2 , and x3 were inde-
pendent variables in the process.
Response surface analysis was carried out by keeping the two variable constant and changing the
single variable to observe the synergetic effect of the variable. The significance of variables and their
interaction with respect to the response were estimated using ANOVA (analysis of variance). The
statistical parameters used to evaluate the model are given in Equation (2) to (9).
Pn   
i¼1 yp;i  yp;ave ye;i  ye;ave
R ¼ qffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffi
Pn  2 Pn  2 (2)
i¼1 y p;i  y p;ave  n¼1 y e;i  y e;ave

Pn  2
ye;i  yp;i
R ¼ 1  Pn
2 n¼1
 2 (3)
n¼1 yp;i  ye;ave
 
n1
Adjusted R ¼ 1  ð1  R Þ 
2 2
(4)
nk1

1 Xn  2
MSE ¼ yp;i  ye;i (5)
n n¼1

rffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffi
1 Xn  2
RMSE ¼ yp;i  ye;i (6)
n n¼1

1 Xn  
MAE ¼ y  yp;i 
n¼1 e;i
(7)
n
RMSE
SEP ¼  100 (8)
ye;ave
 
1 Xn ye;i  yp;i 
MRPD ¼  100 (9)
n n¼1 ye;i
where yp;i ; yp;ave ,ye;i ; ye;ave ; n, and k are predicted yield by RSM, average of predicted yield by RSM,
experimental yield, average experimental yield, number of runs, and number of factors. The model
developed by RSM to predict the yield of grapeseed biodiesel was evaluated using the statistical
parameters. Equations (2) to (9) were used to calculate the evaluation parameters. In these, the
6 H. VENKATESAN ET AL.

Table 1. Comparison of the observed and predicted yield of the trans-esterification process.
Methanol to Oil Molar Ratio Catalyst Concentration
(v/v) Reaction Duration (h) (wt%) Experiment Value RSM Value
0.17(−1) 1.5(+1) 0.45(−1) 89.2 89.458
0.1154566(-α) 1(0) 0.90(0) 93.6 93.275
0.25(0) 1(0) 1.656807(+α) 93.5 93.713
0.3845434(+α) 1(0) 0.9(0) 95.5 95.786
0.25(0) 1(0) 0.9(0) 97 97.184
0.25(0) 1(0) 0.143193(-α) 89.5 89.248
0.25(0) 1(0) 0.9(0) 97.4 97.184
0.25(0) 1.840896415(+α) 0.90(0) 92.1 91.74
0.33(+1) 1.5(+1) 0.45(−1) 91.6 91.851
0.25(0) 1(0) 0.90(0) 97.4 97.184
0.25(0) 1(0) 0.90(0) 96.7 97.184
0.25(0) 0.159103585(-α) 0.9(0) 88.5 88.82
0.33(+1) 0.5(−1) 1.35(+1) 92.1 91.87
0.17(−1) 0.5(−1) 1.35(+1) 91.5 91.27
0.17(−1) 0.5(−1) 0.45(−1) 88.8 89.02
0.33(+1) 0.5(−1) 0.45(−1) 91.8 91.515
0.33(+1) 1.5(−1) 1.35(+1) 95.1 94.9
0.25(−1) 1(0) 0.9(0) 97.2 97.184
0.17(−1) 1.5(+1) 1.35(+1) 94.1 94.412
0.25(0) 1(0) 0.90(0) 97.4 97.184
where α is the axial point at the coded level of 1.618.

Table 2. Independent variables and coded levels.

Coded levels -α −1 0 +1 +α
Molar ratio 0.1154566 0.17 0.25 0.33 0.3845434
Catalyst concentration 0.143193 0.45 0.90 1.35 1.65681
Reaction time 0.15104 0.50 1.00 1.50 1.8409

parametric value of R, R2, and AdjustedR2 was close to 1 and the value of mean square error (MSE),
root mean square error (RMSE), Mean Absolute Error (MAE), standard error percentage (SEP), and
mean relative percent deviation (MRPD) was close to zero as indicated in Table 5.

Results and discussion

Biodiesel was produced from grapeseed bio-oil through transesterification reaction by optimizing the
variable operating parameters such as reaction duration, catalyst concentration, reaction temperature,
and methanol to oil molar ratio. In order to acquire the maximum biodiesel yield, the transesterification
process was carried out with different proportions of methanol to oil molar ratio, catalyst concentration, and
reaction time, while the mixing intensity and reaction temperature were kept constant. Transesterification
process was initiated with 100 ml of oil, appropriate methanol to oil molar ratio (0.11545, 0.17, 0.25, 0.33,
and 0.3845), and catalyst concentration (0.143, 0.45, 0.90, 1.35, and 1.657 gm in oil), reaction duration (0.5,
1, and 1.5 h) at constant rotational agitation speed (500–600 rpm), and constant temperature (60°C). Luque-
Rodrıguez, Luque de Castro, and Perez-Juan (2005) suggested that the reaction temperature between 55°C
and 60°C was ideal to convert raw grapeseed oil into its biodiesel. Moreover, the boiling point of n-hexane
which was used as a solvent during the bio-oil extraction process also lies between 60°C and 68°C. Therefore,
an optimal reaction temperature of 60°C was adopted in this study. Literature reports (Mostafaei (2018) and
Antolin et al. (2002)) also suggested that the transesterification reaction between 60°C and 62°C yielded
maximum FAMEs at variable input process parameters. RSM was employed to optimize the transesterifica-
tion procedure and CCRD was developed to design the experiment and determine the number of
experimental trials. A three-factor five-level experimental design was used. The maximum yield of grape-
seed bio-oil methyl ester of 97.4% was obtained at a catalyst concentration of 0.9 g, a reaction time of 60 min,
and methanol to oil molar ratio of 0.25.
 ENERGY SOURCES, PART A: RECOVERY, UTILIZATION, AND ENVIRONMENTAL EFFECTS 7

Effect of methanol to oil molar ratio

The significant parameter which affected the yield of biodiesel was the methanol to oil molar ratio.
The escalation in the methanol to oil molar ratio led to the rise in biodiesel yield. Maximum yield
(97.4%) of biodiesel was found at 0.25. The yield of biodiesel augmented when the methanol
concentration increased from 0.18% to 0.25%. But, when the methanol to oil molar ratio reached
the highest value 0.384, there was a decline in the yield of biodiesel. On increasing the supply of
methanol more than the optimal quantity, it led to dilution of reaction mixtures and resulted in the
deterioration of effectiveness of the catalyst which ultimately reduced the yield of biodiesel (Hariram
and Bharathwaaj 2016)

Effect of catalyst concentration

Catalyst concentration had a direct influence on the yield of biodiesel. The yield of biodiesel
augmented with the increase in the catalyst concentration. The maximum yield of biodiesel yield
was found at the catalyst concentration of 0.90 g of NaOH. The yield of biodiesel escalated sharply
with an increase of catalyst from 0.45 g to 0.90 g. When the catalyst concentration reached 1.35 g,
a negative appreciation was noticed in the yield of biodiesel. FAME’s formation decreased with the
excess catalyst which led to the hydrolysis of the esters, and a reverse reaction resulted in the
formation of soap and sludge (Hariram and Vasanthaseelan 2015)

Effect of reaction duration

The experiment was performed with five different time durations – 9.54 min, 30 min, 60 min, 90
min, and 110.46 min (0.159 h, 0.5 h, 1 h, 1.5 h, and 1.84 h). Based on the experimental results, it was
found that the maximum yield of biodiesel (97.4%) was noticed at the reaction duration of 60 min
and the lowest biodiesel yield of 88.5% was found at the time of 9.57 min (0.159 h). It can be
understood that the increase in reaction duration enhanced the yield of biodiesel. A significant
upsurge in biodiesel yield was seen as the reaction duration increased from 30 min to 60 min. On the
other hand, a decrease in the FAME formation was also noticed on further increasing the reaction
time beyond 90 min which may be due to the reversible transesterification reaction (i.e., the
hydrolysis reaction) taking place after it reaches the optimal value. It was also noted that the
biodiesel yield was very low at lowered reaction duration, since sufficient time duration was provided
to initiate the transesterification process to convert the mono-alkyl triglyceride into FAMEs
(Venkatesan et al., 2017b).

Grapeseed oil esterification process – RSM approach

The transesterification experiment was executed as per the CCRD experimental design, and the
regression analysis was carried out using RSM. The model equation in terms of the variable
parameters is given in Equation 10 and 11.
y ¼ b0 þ b1 x1 þ b2 x2 þ b3 x3 þ b11 x12 þ b22 x22 þ b33 x32 þ b12 x1 x2 þ b13 x1 x3 þ b23 x2 x3 (10)
where “y” represented the biodiesel yield with respect to the methanol to oil molar ratio, catalyst
concentration, and reaction duration; b1 , b2 , and b3 were linear coefficients; b11 , b22 , and b33 were
quadratic coefficients; b12 , b13 , and b23 were interactive coefficients; and x1 , x2 , and x3 were
independent variables.
y ¼ 63:04314 þ 95:13385x1 þ 21:17361x2 þ 18:71924x3  13:19444x1 x2  0:625x1 x3
þ 3:0x2 x3  146:60416x12  9:95854x22  9:76347x32 (11)
8 H. VENKATESAN ET AL.

Table 3. ANOVA data’s for response surface methodology.

Sum of
Source Squares df Mean Square F-Value P-Value
Model 183.30 9 20.37 141.92 <0.0001 significant
A-MOR 7.61 1 7.61 53.04 <0.0001
B-CC 24.06 1 24.06 167.66 <0.0001
C-TI 10.29 1 10.29 71.70 <0.0001
MOR*CC 1.81 1 1.81 12.58 0.0053
MOR*TI 0.0050 1 0.0050 0.0348 0.8557
CC*TI 3.65 1 3.65 25.40 0.0005
MOR*MOR 12.69 1 12.69 88.40 <0.0001
CC*CC 58.61 1 58.61 408.38 <0.0001
TI*TI 85.86 1 85.86 598.28 <0.0001
Pure error 0.4083 5 0.0817 - -
Lack of fit 1.03 5 0.2054 2.51 0.1672 not significant
R2 0.9962 - - - -
Adjusted R2 0.9922 - - - -
CV % 0.4052 - - - -

The statistical significance of the model was analyzed by the ANOVA test. The model had an F-value
of 141.92 and p-value of 0.0001 which illustrated the model to be substantial with the self-reliance level of
95% (p < 0.05). Both the linear and quadratic parameters had a significant effect on FAME yield. x1 , x2;
x3 , x12 , x22 ; x32 , x1 x2 , and x2 x3 had its p-value less than 0.05 which depicted that it also has a significant
effect on the yield of biodiesel. Considering the individual parameters, catalyst concentration was found
to have more effect on the biodiesel yield which was followed by the reaction duration and methanol to
oil molar ratio. It was observed that all the individual parameters and its squares values had a significant
effect on the biodiesel yield (p < 0.05). The interaction of molar ratio with catalyst concentration and
catalyst concentration with reaction duration had a strong effect on the yield of grapeseed biodiesel
which was significantly evidenced, while the interaction of molar ratio with catalyst concentration had
a lesser effect on the FAME yield and found not significant (p > 0.05). The variation in data can be
observed with a lack of fit value. The lack of fit was found to be not significant with a p-value of 0.1672
(p > 0.05), which denoted that the actual experimental data fit well with the predicted data of the RSM
model and the fitness of the model can be tested with correlation of coefficient which was evaluated. As
suggested in the literature, the correlation of coefficient should be greater than 0.80 for a good fit of the
model. In this developed RSM model, the correlation of coefficient was 0.996, portraying it to be a better
model along with the marginal difference between the R2 and AdjustedR2 which depicted the model to be
significant. Table 3 represents the data pertaining to the ANOVA of the developed RSM model.
Methanol to oil molar ratio of 0.25 and catalyst concentration of 0.90 gm in bio-oil with a reaction
duration of 1 h exhibited maximum yield of grapeseed biodiesel as 97.4% aligning with the prediction of
RSM. The maximum grapeseed biodiesel yield predicted by RSM was 97.18% with an error of about 0.22%.
This prediction confirmed the efficacy of the developed RSM model and second-order mathematical
equation was used for the development of the RSM model. The comparison of the observed and predicted
yield of the trans-esterification process is tabulated in Table 1.

Impact of methanol to oil molar ratio and catalyst concentration using RSM
The yield of grapeseed biodiesel was significantly affected by the interaction between the two variables, i.e.,
methanol to oil molar ratio and catalyst concentration. The combination of reduced catalyst concentration
and methanol to oil molar ratio showed that it had a significant effect on depreciating the biodiesel yield.
When both the molar ratio and catalyst concentration were low, the yield of biodiesel was also noticed to be
lower. In this study, higher catalyst concentration and higher methanol to oil molar ratio also had a negative
consequence on the biodiesel yield as shown in Figure 3. From the experiment trials, it can be observed that
maximum biodiesel yield was evidenced when both the catalyst concentration and methanol to oil molar
 ENERGY SOURCES, PART A: RECOVERY, UTILIZATION, AND ENVIRONMENTAL EFFECTS 9

Figure 3. Impact of molar-ratio and catalyst concentration at varying reaction duration (a, b and c) and the impact of reaction
duration and molar-ratio at varying catalyst concentration (d, e and f) on biodiesel yield

ratio were 0.9 g of NaOH and 0.25, respectively. The synergetic effect between the parameters can be
understood by altering any one parameter keeping the other as constant. Primarily, the catalyst concentra-
tion was kept constant and methanol to oil molar-ratio was varied and noticed that maximum grapeseed
biodiesel was predicted between 0.25 and 0.325. The biodiesel yield decreased when molar ratio was further
increased beyond 0.325. Furthermore, the methanol to oil molar ratio was kept constant, and the influence
of catalyst concentration on the biodiesel yield was also observed. The grapeseed biodiesel yield increased
and reached maximum when the catalyst concentration increased and was maintained between 0.9 and 1.15
gm. Based on this analysis, it can be inferred that increase in both catalyst and molar ratio above the optimal
level significantly decreased the yield of grapeseed biodiesel which may be due to the hydrolysis reaction
initiated in the test sample and soapy sludge formation as a result of higher NaOH concentration. As can be
seen in Figure 3a-c, the synergetic effect of catalyst concentration and methanol to oil molar ratio was
10 H. VENKATESAN ET AL.

visualized during 30 min, 60 min, and 90 min of reaction duration. There is a notable rise in grapeseed
biodiesel yield with the escalation in reaction time up to to a certain duration, and upon exceeding the
optimum range, the molecular interaction between NaOH and methanol created a reverse reaction resulting
in the decreased yield of grapeseed biodiesel.

Impact of molar ratio and reaction time using RSM

The synergetic effect between the reaction duration and molar ratio can be witnessed in Figure 3d-f. The
yield of grapeseed biodiesel was observed to be lower when both the reaction time and methanol to oil
molar ratio were reduced. There was a corresponding rise in the yield of biodiesel when both the process
operating parameters were increased gradually. It was noted that the effect of reaction time was
significant on the FAME formation when compared to the methanol to oil molar ratio when the catalyst
concentration was maintained at low levels as shown in Figure 3. Lower grapeseed biodiesel yield with
decremented molar ratio and reaction duration may be due to lesser time availability for the conversion
of mono-alkyl triglyceride into FAMEs of grapeseed oil. From experimental trials, maximum biodiesel
yield was noticed when both the reaction duration and methanol to oil molar ratio were 60 min and 0.25,
respectively. The biodiesel yield continued to upsurge with an increase in molar ratio and reaction time
and attained maximum value at molar ratio between 0.26 and 0.31 and reaction time between 60 and 72
min. Further increase in reaction duration and molar ratio deteriorated the FAME formation and
thereby reduced the yield of grapeseed biodiesel. Increase in methanol concentration along with
prolonged reaction duration favored reversible transesterification reaction; thereby a higher yield of
biodiesel was affected significantly. Figure 3d-f portrays the effect of methanol to oil molar ratio and
reaction time on biodiesel yield at catalyst concentration of 0.45 g, 0.90 g and 1.35 g of NaOH. It can be
inferred that, with the intensification in catalyst concentration, there was an increase in the grapeseed
biodiesel yield, but when the concentration crossed the optimum range, the biodiesel formation
detoriates due to the sludge formation at augmentation concentration in the catalyst.

Effect of reaction duration and catalyst concentration using RSM

Figure 4 depicts the synergetic effect between reaction duration and catalyst concentration on the
biodiesel yield of grapeseed oil. It is evidenced that when both the catalyst concentration and
reaction duration were escalated, the grapeseed biodiesel yield also increased. The highest yield of
97.4% was noticed when both the catalyst concentration and reaction duration of 0.90 g of NaOH
and 60 min, respectively. Varying one of the process operating parameters with the other as constant
describes there interactions. Likewise, lower grapeseed biodiesel yield was noticed when lowering
both the catalyst concentration and reaction duration which may be due to shortage of time for the
transesterification process to initiate and convert the mono-alkyl triglycerides into FAMEs. On the
other hand, upsurging the catalyst concentration and reaction duration above the optimal level
enhanced the tendency of soapy formation. The grapeseed biodiesel yield increased with the upsurge
of reaction duration and molar ratio as shown in Figure 4. Maximum yield of biodiesel was noticed
between the molar ratio of 0.26 and 0.31 and reaction duration of 1.0 and 1.2 h. Further increase in
both the operating parameters led to a decrement in the biodiesel yield. Similarly, an increase in the
methanol concentration above the optimum value led to the reversible reaction forming the soap
which reduced the FAME yield greatly. From Figure 4a-c, it can be noticed that the yield of biodiesel
had a significant effect on catalyst concentration and reaction duration with variations in methanol
to oil molar ratio as 0.17, 0.25, and 0.35. With the increase in the molar ratio, the yield of biodiesel
improved notably up to the optimal level, but deteriorates later. Excess addition of the methanol led
to the hydrolysis reaction of oil, which had negative improvement on the grapeseed biodiesel yield.
 ENERGY SOURCES, PART A: RECOVERY, UTILIZATION, AND ENVIRONMENTAL EFFECTS 11

Figure 4. Impact of catalyst concentration and reaction time at varying molar-ratio (a, b and c) on yield of grape seed biodiesel

Optimization of process parameters

The statistical parameters for the given model have been formulated and applied to understand the
predictive capability of the model. The MSE, RMSE, SEP, MAE, and MRPD were calculated based on
Equations (2) to (9). The statistical parameters, R and R2, were found to have close proximity with
each other, which confirmed that the developed model possesses a higher accuracy in predicting the
yield of grapeseed biodiesel. Based on the R2 value, it was assessed that the variation and accuracy of
99.2% can be expressed in the model. The MSE and RMSE indicated the closeness of the predicted
and actual data points, while the SEP, MAE, and MRPD indicated the accuracy and precision of the
prediction. As the statistically significant parameter value should be closer to zero for a good fit, the

Table 4. Statistical parameters

to evaluate the model predictive
capability.
Parameters RSM
R 0.996
R2 0.992
AdjR2 0.9852
MSE 0.07175
RMSE 0.26786
SEP% 0.286
MAE 0.253
MRPD 0.2717
12 H. VENKATESAN ET AL.

Table 5. Comparison of experimental and RSM predicted

results in yield of maximum grapeseed biodiesel.
Parameters Values
Molar ratio (in v/v) 0.2758
Catalytic concentration (in g/g) 1.045
Reaction duration (in h) 1.11
Predicted value (in %) 97.62
Experimental value validation (in %) 97.7
Residual 0.08
MRPD (in %) 0.082

values of MSE, RMSE, SEP, MAE, and MRPD value as tabulated in Table 4 signified its importance
as it showed a minor deviation from the actual experimental value.
From the statistical parameters as presented in Table 4, it can be understood that the developed
model was good to predict the optimum process parameters and to obtain the maximum yield of
grapeseed biodiesel. The developed RSM model predicted the maximum yield of grapeseed biodiesel
(97.62%) which will be achieved at a catalyst concentration of 1.045 g (NaOH), molar ratio of 0.2758,
and a reaction duration of 1.11 h as shown in Table 5. Figure 5a-c depicts the interactive effect of the
variable process parameters of the RSM model. Moreover, the transesterification process was
conducted with the predicted parameters of RSM to validate the developed model. The experimental

Figure 5. RSM predicted maximum biodiesel yield at molar-ratio and catalyst concentration when reaction time -1.11042 hour (a),
reaction time and molar-ratio at catalyst concentration-1.045 g (b), catalyst concentration and reaction time at molar-ratio-0.2758
v/v (c)
 ENERGY SOURCES, PART A: RECOVERY, UTILIZATION, AND ENVIRONMENTAL EFFECTS 13

trial yielded 97.7% of grapeseed biodiesel, which was in correlation with the predicted data of the
RSM model with a residual of 0.08. From this, it can be understood that RSM can be used to predict
the yield of grapeseed biodiesel, and the synergetic effect of the variable operating parameters can be
analyzed. Furthermore, analysis with the RSM approach, predicted the maximum bio-diesel produc-
tion at molar ratio and catalyst concentration when reaction time was −1.11042 h, reaction time and
molar ratio at catalyst concentration 1.045 g, catalyst concentration and reaction time at molar ratio
0.2758 v/v at reaction temperatures 65°C and 70°C showcased a marginally negative result with
a deteriorated FAME production by 1.6% at 96.1% transesterification efficiency. This may be due to
the reversible catalytic reaction of the transesterification process above 60°C reaction temperature
and vaporization of methanol which is having a boiling point of 64.5°C (John and Seralathan 2019).
Figure 6 shows the regression graph for understanding the proximities of the developed RSM model
and the actual experimental trials on the yield of grapeseed biodiesel. The closeness of the predicted
data to the fit line signifies the goodness of the fit less with lesser deviation from the actual value.
The physiochemical properties of grapeseed biodiesel such as kinematic viscosity, calorific value,
fire and flash point, density, and acid values were determined as per the American Society of Testing
and Materials Standards and the values were compared with the standards in Table 6. Kinematic
viscosity is one of the most important properties of the biodiesel as it directly influences the fuel
atomization characteristics and also a higher viscous fuel will affect the fuel distribution inside the
combustion chamber. As per the ASTM D445 standards, the viscosity of the fuel should be between
3.5 and 5 cSt. The kinematic viscosity of grapeseed biodiesel was 4.04 which was within the ASTM
limits. The flashpoint of the biodiesel should be higher than the 101°C as per the ASTM D93. The

Figure 6. Regression graph for experimental data and predicted data using RSM

Table 6. Physiochemical properties of grapeseed bio-oil and its biodiesel.

Fuel Property ASTM Standards Grapeseed Bio-Oil Grapeseed Biodiesel ASTM Biodiesel Standards
Density at 15°C (in kg/m3) ASTM D792 905.7 880.2 860–900
Kinematic viscosity at 40°C (in cSt) ASTM D445 26.62 4.04 3.5–5.0
Flash point (in °C) ASTM D93 230.7 124 101–130
Acid value (in KOH/g) ASTM D664 1.4 0.36 > 0.5
Cetane number ASTM D613 - 54 47–51
Calorific value (MJ/kg) ASTM D6751 37.7 39.52 36.5–41
Ester content ASTM D7029 - 96.2 -
Iodine number (in g/100g) ASTM D5902 104.2 104.2 -
Oxygen content (in %) ASTM D4944 8 11 2.5–12
14 H. VENKATESAN ET AL.

flashpoint of the grapeseed biodiesel was around 124°C. The density of fuel was estimated to be
880.2 kg/m3. The cetane number, one of the important parameters of the fuel, has to be in the
optimum range for an efficient combustion. The cetane number should have a minimum value of 47
as per the ASTM D613. The acid value of the biodiesel should be lesser than 0.5 as per the ASTM
D664. The acid value of the biodiesel was around 0.36 mg of KOH/g which met the ASTM
standards. The FAME content was estimated to be 96.2% in grapeseed biodiesel by ASTM D7029
method. The iodine value in both grapeseed bio-oil and its biodiesel was determined as 104.2 g/100g.
The water content of grapeseed biodiesel was estimated as 0.03%.

Conclusion
RSM model was successfully developed to predict the yield of grapeseed biodiesel by varying the process
operating variables in the single-stage transesterification process. Single-stage transesterification was
performed since the acid value was <2 mg of KOH/g. The yield of grapeseed biodiesel was significantly
influenced by parameters such as reaction duration, methanol to oil molar ratio, and catalyst concen-
tration. The experiments were performed in accordance with the CCRD design at a reaction tempera-
ture of 60°C and agitation speed of 450 rpm. RSM illustrated the synergetic interactions between
reaction duration, catalyst concentration, and molar ratio, which revealed its significance in the grape-
seed biodiesel. The interaction between molar ratios and reaction duration had a lesser influence on the
yield of biodiesel. The increase in molar ratio above the optimal range decreased the effectiveness of the
catalyst, and, on the other hand, increase in the catalyst concentration more than optimum level
resulted in sludge formation which eventually decremented the biodiesel yield.
The significance of the variable parameters on the yield of grapeseed biodiesel has been assessed
through ANOVA. The accuracy and fitness of the developed quadratic RSM model were estimated
using the statistical parameters such as R; R2 , MSE, RMSE, SEP, MAE, and MRPD and found to be
accurate and efficient in predicting the yield of Grapeseed biodiesel. RSM model predicted
a biodiesel yield of 97.62% with a catalyst concentration of 1.045 g, methanol to oil molar ratio of
0.2758, and reaction duration of 66.6 min at a constant agitation speed of 450 rpm and temperature
60°C which was also validated experimentally. The biodiesel properties such as calorific value,
density, kinematic viscosity, flashpoint, fire point, acid value, water content, and iodine value were
estimated and it satisfied the ASTM standards. Finally, this study recommends the grapeseed
biodiesel as the potential feedstock for the production of biodiesel.

Nomenclature and Abbreviation

CCRD central composite rotatable design
ANN artificial neural network
ANFIS adaptive neurofuzzy interference
RSM response surface methodology
FAME fatty acid methyl esters
RMSE root mean square error
FAEE fatty acid ethyl esters
FFA free fatty acids
MAPD mean absolute percent deviation
CCD central composite design
MRPD mean relative percent deviation
MSE mean square error
R2 Coefficient of determination
R Correlation coefficient
MOR Molar ratio
CC catalyst concentration
TI reaction time
ANOVA analysis of variance
MF membership function
 ENERGY SOURCES, PART A: RECOVERY, UTILIZATION, AND ENVIRONMENTAL EFFECTS 15

SEP standard error percentage

Notes on contributors
Hariram Venkatesan holds a doctoral degree from Anna University Chennai, India. He finished his masters in
Automobile Engineering from the same institution. His research interest includes Bio-energy and Engine Combustion.

Bose A is a Post graduate student in the Department of Mechanical Engineering, Hindustan Institute of Technology
and Science, Chennai, India.
Seralathan Sivamani holds a doctoral degree from Hindustan Institute of Technology and Science, Chennai, India.
He completed his masters from IIT Madras. His research interest includes Energy, Turbo machines and Wind
turbine.

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