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Enhancement of biodiesel production from waste cooking oil: ultrasonic-

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Enhancement of biodiesel production from waste

cooking oil: ultrasonic- hydrodynamic combined
cavitation system

Mahrokh Farvardin, Bahram Hosseinzadeh Samani, Sajad Rostami, Ahmad

Abbaszadeh-Mayvan, Gholamhassan Najafi & Ebrahim Fayyazi

To cite this article: Mahrokh Farvardin, Bahram Hosseinzadeh Samani, Sajad Rostami,
Ahmad Abbaszadeh-Mayvan, Gholamhassan Najafi & Ebrahim Fayyazi (2019): Enhancement
of biodiesel production from waste cooking oil: ultrasonic- hydrodynamic combined cavitation
system, Energy Sources, Part A: Recovery, Utilization, and Environmental Effects, DOI:
10.1080/15567036.2019.1657524

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ENERGY SOURCES, PART A: RECOVERY, UTILIZATION, AND ENVIRONMENTAL EFFECTS
https://doi.org/10.1080/15567036.2019.1657524

Enhancement of biodiesel production from waste cooking oil:

ultrasonic- hydrodynamic combined cavitation system
Mahrokh Farvardin a, Bahram Hosseinzadeh Samani a
, Sajad Rostami a,
Ahmad Abbaszadeh-Mayvan b, Gholamhassan Najafi c
, and Ebrahim Fayyazi c

a
Department of Mechanical Engineering of Biosystem, Shahrekord University, Shahr-e Kord, Iran; bBiosystems
Engineering Department, Gorgan University of Agricultural Sciences and Natural Resources, Gorgan, Iran;
c
Department of Biosystems Engineering, Tarbiat Modares University, Tehran, Iran

ABSTRACT ARTICLE HISTORY

Concerning the growing need for energy resources and reduction of fossil Received 20 June 2019
fuels, researchers seek for the use and development of biofuels. Among the Revised 12 August 2019
biofuels, biodiesel has captured the attention of researchers since it deals Accepted 14 August 2019
with the oil cost and embraces environmental benefits. Aiming at contin-
KEYWORDS
uous and optimal biodiesel production, the current study examines the Hydrodynamic; ultrasound;
effects of the residence time of hydrodynamic reactors, catalyst concentra- biodiesel; waste cooking oil;
tion, methanol-to-oil ratio, and ultrasound power on methyl esters yield. To response surface method
optimize the transesterification reaction of the waste oil, the response
surface method was used. Results of the study indicated that the increase
of residence time results in an increase of the methyl esters yield, but
following the time up to 90 s, the methyl esters yield decreases. The
increase of catalyst by 1% leads to the increase of the methyl esters yield,
and up to 1.25% the catalyst concentration, the methyl esters yield
decreases by 7%. The increase of methanol-to-oil ratio up to 6:1 results in
an increase of yield, and up to 8:1 methanol-to-oil ratio, the methyl esters
yield follows an increasing trend with a slight slope. The optimal conditions
in this study were 60 s residence time, 1% catalyst concentration, 6:1
methanol-to-oil ratio, and 250W ultrasound power, and that the methyl
esters yield, as well as the consumed energy, were obtained 90.45% and
21.52 kJ, respectively. In conclusion, the suggested method is suitable for
biodiesel production based on the methyl esters yield and energy
consumption.

Introduction
Biodiesel is an important biofuel due to its environmental benefits, but its production in large scale
still requires to optimize the production using waste material. Wastes, residues of food, distilled
materials, and the sewage can be good resources for producing vegetable oils (Demirbas 2009; Neam,
Al-Layla, and Sedeeq 2019; Pinzi et al. 2009; Rajak and Verma 2018). The most important advan-
tages of vegetable oils are their renewability and environment-friendly aspects which cause that there
is no concern for the completion of their resources. The use of biodiesel as pure or mixed by diesel
reduces the level of pollution significantly compared to diesel (Moser 2009; Shirneshan, Samani, and
Ghobadian 2016).
Currently, biodiesel and diesel are mixed by a different percentage. The mixture is a function of
economic conditions, adopted environmental regulations, ability, and capability of applied materials,
and combustion characteristics. The thermal value of vegetable oils is quite similar to that of the

CONTACT Bahram Hosseinzadeh Samani b.hosseinzadehsamani@gmail.com Department of Mechanical Engineering of

Biosystem, Shahrekord University, Iran
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 M. FARVARDIN ET AL.

diesel, thus attentions have been drawn toward the production of biodiesel from vegetable oils
(Azadi et al. 2017; Dhar, Kevin, and Agarwal 2012; Shuba and Kifle 2018). However, the use of
vegetable oils in direct-injection diesel engines is impossible due to some physical properties of these
oils. Of the retracing characteristics is high viscosity of the vegetable oils. The effects of high
viscosity, in case of using in diesel engines, are improper atomization of fuel, incomplete combus-
tion, and sedimentation in the injection. These problems can be resolved through diluting with
suitable solvents, emulsifying, pyrolysis (thermal decomposition or breaking of large molecules by
heat), and transesterification. It is worth mentioning that transesterification is the most important
method among the methods mentioned above (Fadhil, Al-Tikrity, and Ibraheem 2019; Fayyazi et al.
2014; Guan and Kusakabe 2009).
The transesterification reaction is the reaction of vegetable oils in the presence of a catalyst (acid,
base, enzyme) with alcohol (mostly methanol and ethanol) which leads to produce methyl esters
(biodiesel) and glycerin. This reaction is performed faster in the presence of a base catalyst (Nie
2012). Methyl or methyl esters can be produced from the plant and trees oils, animals fat, or from
the waste oils (Hosseinzadeh 2016; Samani et al. 2016). The cost of biodiesel production is the major
barrier to its commercial production, and the use of waste oils, conformation to a continuous
transesterification reaction, and high-quality glycerin recycling are among the cases which reduce the
cost of biodiesel production. Indeed, the quality of biodiesel produced from waste oils equals the
quality of biodiesel produced from the vegetable oils. To choose the optimal conditions for this
reaction with an aim to reduce the time as well as increase the efficiency of this reaction, several
studies have been undertaken (Fayyazi et al. 2014; Milano et al. 2018; Samani et al. 2016).
Traditionally, the transesterification reaction requires continuous mechanical stirring for 45 min
to 55 min since the reaction between alcohol and oil is only possible at the interface between the two
liquids (on the molecular scale) (Anwar and Rashid 2007).
In general, the mixture of alcohol and triglycerides is of incompatible type, therefore, the low
contact surface of reactants with one another results in slowing the rate of the transesterification
reaction. Adding catalyst to the reactants results in the improved contact surface of reactants (resolving
the problems dealing with alcohol and triglyceride incompatibility), thus leading to increased reaction
rate and increased level of produced biodiesel (Hosseinzadeh 2016). In the process of transesterifica-
tion, researchers have reported different intensification reactors such as the centrifuge contactors,
shear, reactive distillation, cavitation (hydrodynamic and ultrasonic), and etcetera reactors. Reactors
are used in most of the systems such as production and energy conversion. Cavitation reactors cause
the intensification of mass transfer rate and thermal transformation of chemical processes through
creating local disturbances and microcirculation within the reactor (Qiu 2010).
Hydrodynamic cavitation reactors cause a shear force in liquid and micro bubble formation as
well as collapse due to the existence of cavitation on the rotor and circulation of fluid between the
rotor and stator with high speed (Chuah et al. 2015b; Ghayal, Pandit, and Rathod 2013). Fluid
circulation with high speed in these reactors increases the level of stirring and progression of
reaction rate which causes a reduction of production time and an increase of efficiency. In the
case of ultrasonic cavitation reactors, when the ultrasound waves move across the liquid, there is
a liquid movement in the opposite direction of the ultrasound waves (Behruzian et al. 2018;
Hosseinzadeh Samani et al. 2018). The sound energy is converted to the kinetic energy, and such
an effect is independent of the cavitation phenomena. The sound waves help the thermal and mass
transfer in liquid. Such an effect facilitates the ultrasound energy distribution and heat scattering
(Abbaszadeh-Mayvan et al. 2018; Knothe 2005). In addition to this effect, the heat of liquid is
produced as the result of shear between the interface levels, such as the surface between probe metal
and liquid, which is among the desired factors in the transesterification reaction.
In general, the flows and performed cavitation lead to the mixture of oil and methoxide
(combined methanol and catalyst) phases, resulting in increased stirring and reaction rate. The
objective of the current study is to examine and develop a combined ultrasonic-hydrodynamic
system for continuous biodiesel production from the waste cooking oil. The combination of
 ENERGY SOURCES, PART A: RECOVERY, UTILIZATION, AND ENVIRONMENTAL EFFECTS 3

ultrasonic and hydrodynamic is the first report, and cause to improve mixing of methoxide and oil
before the entrance to the hydrodynamic reactor.

Materials and methods

Materials
To produce biodiesel using the base transesterification method, the waste edible oils were collected
from Shahrekord University and were used as the primary raw material. To prepare the oil for
introducing to the biodiesel process, the oils were prepared prior to the initiation of the reaction.
Two important factors, namely, lack of water and excess materials (such as the food piece or any other
material) were considered using dewatering and filtering processes in the oil (Chau et al., 2015a). For
purification, the waste cooking oil was kept in a hollow container for a few days so that large parts of
the impurities could be deposited during this period. The oil was then passed through a 500 µm filter
for purification. Water deposition method was used for dewatering (drying) of waste oil. Since the
water density is higher than the oil density, the water was separated from the oil over time. Under
normal condition, this is very time-consuming. Therefore, to accelerate the separation, the oil was
heated to 60°C for 15 minutes and, after heating, the oil was transferred to the drainage tank for
24 hours and water was separated from it. The alcohol and catalyst used in this study were Methanol
Alcohol (99.9%, Merck, Germany) and Potassium hydroxide (99.8%, Merck, Germany).

A combined ultrasonic- hydrodynamic system

The combined ultrasonic-hydrodynamic system consists of the following components (Figure 1):
1-rotor 2- stator 3- temperature regulator (circulator) 4- ultrasonic stirrer 5-peristaltic pump 6-
electro-motor 7- connecting pipes.

Figure 1. Schematic of the ultrasonic-hydrodynamic system for biodiesel production.

4 M. FARVARDIN ET AL.

The ultrasonic (Mafoghe-Sot company, 400W, Iran) was used at 100, 250 and 400 watts, and the
diameter of the ultrasound probe was 12 mm (Ansari Samani et al. 2019). The hydrodynamic reactor
consists of a rotor and a stator. In the laboratory scale of this system, a polycarbonate stator is
considered so that the transesterification process gets visible. The rotor is made of stainless steel and
there are cavities made on it to produce bubbles or cavities along their edges. In this reactor, the
rotor receives its propulsion power from an electromotor which must be fully fitted and sealed with
its connections and components. The electromotor used in this system was a type of Ronix engine
with a gearbox power output and speed of 750 W and 3200 RPM, respectively.

The method of biodiesel production in the developed system

First, methanol (CH3OH) was mixed with homogeneous potassium hydroxide (KOH) catalyst by the
stirring method, leading to the formation of methoxide solution and methoxide solution. Then, this
solution was added to the ultrasonic reactor. During this stage, the cavitation occurs and the
emulsion of oil and methoxide is formed. The emulsion formed by the peristaltic pump is introduced
into the chamber between the rotor and the stator. While the rotor rotates at a constant speed of
3,000 rpm, the fluid flows between the rotor and the stator and encounters the center of the
centrifugal force. The cavities on the rotor result in pressure variations and exertion of the shear
force, resulting in bubbling or cavitation. At the same time, the fluid circulation at high speed causes
the pressure and temperature to rise pointwise in the bubbles, causing burst or collapse in bubbles.
Such a procedure results in the formation of glycerin and methyl ester, as well as some excess
alcohol. The alcohol contained in the transesterification reaction product was recycled by the heat
treatment (boiling point of alcohol) and then, due to the higher density of glycerin compared to
methyl ester, glycerin was isolated from methyl ester by the deposition method. The experiment was
conducted in 30, 60 and 90 seconds.

The method of evaluating the produced biodiesel

After the preparation of the sample and injection into a gas chromatography device based on BS EN
14103 standard, responses were issued by the detector based on the concentration of the compounds
in the sample. Using the Total Chromium software, chromatograms obtained from detectors’
responses were observed and calculations were performed. Chromatogram contains the peaks
corresponding to the concentration of the compounds in the injected sample, including the solvent,
methylated fatty acids, and standard internal. The area under the curve of each peak corresponds to
its concentration in the sample. The methyl ester content of the biodiesel sample (C) is calculated
using the Equation (1) according to BS EN 14103 (Fayyazi et al. 2014):
P
AAIS MIS
C¼  10 (1)
AIS M
Where ∑A is the sum of under peak area of C6 to C24 fatty acids, µV*sec; AIS is the under peak area
of standard internal (Methyl Hepta Decanoate), µV*sec; MIS is the mass of used standard internal
(mg); M is the mass of biodiesel sample (mg).
Oil to the methyl ester yield is calculated by Equation (2) (Fayyazi et al. 2014):

WFAME =MFAME
FAMEð%Þ¼ 100 (2)
3Wwco =Mwco
Where wFAME and wWCO (mg) are produced biodiesel mass and used waste oil mass, respectively.
Also, MFAME and MWCO are mean molecular mass for biodiesel and waste oil, respectively.
 ENERGY SOURCES, PART A: RECOVERY, UTILIZATION, AND ENVIRONMENTAL EFFECTS 5

Table 1. Levels of chosen independent variables in the response surface method.

Coding levels
Independent variables −1 0 1
Reaction time (s) 30 60 90
Catalyst concentration (w/w%) 0.75 1 1.25
Alcohol to oil molar ratio 4:1 6:1 8:1
Ultrasound power (W) 100 250 400

Statistical analysis and optimization of reaction parameters

In this research study, response surface methodology and a Box- Behnken design were used. First,
the dependent variables’ levels according to Table 1 were coded and were based on the selected
method (Hosseinzadeh Samani et al. 2015). All the experiments were replicated three times to
determine the variability of the results and to assess the experimental errors. The reported values
are the average of the individual run. To obtain the optimal value, Equation (3) was used
(Hosseinzadeh Samani et al. 2019; Samani et al. 2016):
X X X
Y i ¼ β0 þ Bi Xi þ βij Xi  Xj þ βjj X2 i þ ε (3)

Where βo ،βi ،ijβ, and βjj are constant coefficients; xi and xj are independent variables in the process;
ε is the random error.

Results and discussion

Properties of the tested oil
Table 2 shows the mixture of used waste oil fatty acids. According to the table, Linoleic and Oleic
fatty acids, with 55% and 23% values, have the maximum share of the fatty acid profile in the
aforementioned oil.

Results of statistical analysis and data modeling

Table 3 showed the analysis of variance of the quadratic regression model for the amount of
biodiesel conversion. The Model F-value of 68.65 implies the model is significant. There is only
a 0.01% chance that a “Model F-Value” this large could occur due to noise. Values of “P-value” less
than 0.0500 indicate model terms are significant. In this case, T, C, M, P, T × C, T × P, C × P, T2,
C2, M2 are significant model terms. Values greater than 0.1000 indicate the model terms are not

Table 2. Chemical and physical properties of the used WCO.

Properties Unit Amount
Density gcm−3 0.905
Kinematic viscosity mPa.s 25.580
Acid value mg KOH/g oil 0.98
Iodine value g I2/100 g oil 112.5
Water content mg g−1 0.15
Palmiticacid (C16:0) wt.% 10.71
Stearic acid (C18:0) wt.% 2.45
Oleic acid (C18:1)* wt.% 22.90
Linoleic acid (C18:2)* wt.% 55.01
Linolenic acid (C18:3)* wt.% 2.67
Other fatty acids wt.% 6.26
Mean molecular weight of WCO g mol−1 876.60
* Carbon atoms number: double bond number.
6 M. FARVARDIN ET AL.

Table 3. ANOVA analysis of variance obtained from the experiment data.

Source Sum of Squares Df Mean Square F Value P-Value
Model 459.45 14 32.82 68.65 < 0.0001
T-Time 25.01 1 25.01 52.32 < 0.0001
C-Catalyst 27.73 1 27.73 58.01 < 0.0001
M-Molar ratio 36.46 1 36.46 76.26 < 0.0001
P-Ultrasonic 5.67 1 5.67 11.86 0.0049
TC 6.24 1 6.24 13.05 0.0036
TM 3.050E-003 1 3.050E-003 6.381E-003 0.9377
TP 3.90 1 3.90 8.15 0.0145
CM 0.93 1 0.93 1.95 0.1875
CP 7.46 1 7.46 15.61 0.0019
MP 2.18 1 2.18 4.56 0.0540
T2 138.61 1 138.61 289.93 < 0.0001
C2 223.42 1 223.42 467.33 < 0.0001
M2 11.66 1 11.66 24.38 0.0003
P2 0.43 1 0.43 0.89 0.3640
Residual 5.74 12 0.48
Lack of Fit 4.93 10 0.49 1.22 0.5317
Pure Error 0.81 2 0.40
Cor Total 465.19 26

significant. If there are many insignificant model terms (not counting those required to support
hierarchy), the model reduction may improve your model. The “Lack of Fit F-value” of 1.22 implies
the Lack of Fit is not significant relative to the pure error. There is a 53.17% chance that a “Lack of
Fit F-value” this large could occur due to noise.
Equation (4) is obtained from the data analysis. R-squared and error standard are 0.9733 and 0.69,
respectively. Considering the variance test of the regression coefficients, non-significant coefficients,
including TM, CM, P2 were excluded from Equation (4), yielding Equation (5):

Y ¼51:1289 þ 0:9464  T þ 196:1231  C þ 4:9279  M  0:0101  P  0:1665

 TC þ 4:60252E  4  TM  2:19344E   TP þ 0:9663  CM þ 0:0364
 CP  2:46083E  3  MP  5:66436E  3  T2  103:5576  C2  0:3695
 M2 þ 1:25552E5  P2 (4)

Y ¼  60:3571 þ 0:9617  T þ 204:9345  C þ 6:2043  M  3:91195E  3

 P  0:1665  TC  2:19344E  4  TP þ 0:0364  CP  2:46083E  3
 MP  5:76899E3  T2  105:0642  C2  0:3931  M2 (5)
Where T is reaction time (s), C is Catalyst concentration, M is the methanol-to-oil ratio, P is the
ultrasonic power and Y is methyl ester yield (%).
For the assumed equation, R-squared and error standard are 0.9735 and 0.69, respectively. Figure (1)
shows proper accuracy of the model obtained from estimating the methyl ester derived per the changes of
independent variables (Figure 2).
To rank the effect of eh variable, the equation was normalized as follows:

Y ¼ þ 90:68 þ 1:44  T  1:52  C þ 1:74  M þ 0:69  P  1:25  TC  0:99  TP

þ 1:37 CP  0:74  MP  5:19  T2  6:57  C2  1:57  M2 (6)

Based on the coefficient values in Equation (6), one can demonstrate that residence time, methanol-
to-oil ratio, ultrasonic power, and catalyst concentration have the maximum effect on producing the
methyl esters, respectively. According to the positive mark of coefficients dealing with the residence
time, methanol-to-oil ratio, and ultrasonic power, it is clear that these three variables are directly
 ENERGY SOURCES, PART A: RECOVERY, UTILIZATION, AND ENVIRONMENTAL EFFECTS 7

Figure 2. Actual data fitting in line with data obtained from the model.
(a) (Molar ratio: 6:1, Ultrasonic power: 250 W) (b) (Catalyst Concentration: 1%, Ultrasonic power: 250 W) (c) (Catalyst
Concentration: 1%, Time:60 s) (d) (Catalyst Concentration: 1%, Molar ratio:1%)

related to the produced methyl esters. This means that higher levels of these factors result in
increased output methyl esters and vice versa. However, due to the negative mark of catalyst
percentage coefficient, this variable has a reverse relationship with the produced methyl esters,
emphasizing that higher catalyst percentage leads to decreased output methyl esters and vice versa.

The effect of independent variables on biodiesel production yield

As Figure (3a) represents, the increase of residence time up to 60s results in an increase of methyl
esters yield, but after this time, the methyl esters yield decreases (Chitsaz et al. 2018). The reason for
following such an increasing trend in the first section is that the increase of residence time leads to
the increase of the effects on reaction mixture at a constant time, and at the same time, the effects of
hydrodynamic reactor cavitation on the reaction environment increase. In contrast, in the second
section, due to the balanced transesterification reaction, the reduction of reactants in the environ-
ment results in reaction’s tendency to the left, leading to the decrease of biodiesel conversion
percentage (Chuah et al. 2015a; Issariyakul and Dalai 2014). Considering the decreased biodiesel
conversion percentage with the increase of time, some researchers have justified the reason as the
fact that glycerin and methanol are both polar and can be dissolved into one another, thus with the
increase of time and more production of glycerin, much more levels of methanol is dissolved in it
and leave the main reaction. Therefore, the reaction turns to the production of methanol and the
efficiency of the main reaction decreases. Other researchers (Capocelli et al. 2014; Mostafaei et al.
2015) have reported similar findings concerning the increase in residence time and a decrease in
performance. It is worth mentioning that the time of reaction with hydrodynamic reactor has
a decreased by 30 times compared to the common reaction time. In fact, this method has a lower
residence time compared to the common non-continuous biodiesel fuel production reactors which
need more than 40min up to 1h time (Ghobadian et al. 2008; Marchetti, Miguel, and Errazu 2007;
Pal and Trivedi 2014). The reason is that the physical effect of the hydrodynamic reactor (cavitation)
lies in better and more emulsion between the insoluble reactants (oil and alcohol) where the increase
of the joint between these reactants, through the created micro-turbulence during cavitation, results
in increased reaction kinetics (Kalva, Sivasankar, and Moholkar 2008).
8 M. FARVARDIN ET AL.

(a) (Molar ratio: 6:1, Ultrasonic power: 250 W)

(b) (Catalyst Concentration: 1%, Ultrasonic power: 250 W)

(c) (Catalyst Concentration: 1%, Time:60 s)

(d) (Catalyst Concentration: 1%, Molar ratio:1%)

Figure 3. The effect of residence time, catalyst percentage, molar ratio, and ultrasound power on methyl ester conversion
percentage.

Also, as Figure (3b) indicates, the increase of catalyst up to 1% results in increased conversion
percentage, and then, the increase of catalyst up to 1.25% leads to 7% decrease conversion percen-
tage. It is worth noting that considering C2 (significant and negative), one can demonstrate that the
increase of methyl esters yield per the increase of catalyst percentage is based on the quadratic
 ENERGY SOURCES, PART A: RECOVERY, UTILIZATION, AND ENVIRONMENTAL EFFECTS 9

function which is downwardly concave. In addition, the increase of catalyst percentage results in
a reduction of performance and saponification of transesterification reaction (Chitsaz et al. 2018;
Chuah et al. 2015a; Hingu, Gogate, and Rathod 2010; Rengasamy et al. 2014).
Figure (3c) shows that the increase of methanol-to-oil ratio results in increased methyl esters yield
trend (Rengasamy et al. 2014). In this trend, there is more slope from 4:1 to 6:1 methanol-to-oil ratio
compared to 6:1 to 8:1 methanol-to-oil ratio which has a slightly increasing slope. Considering the
significance of M2 in the model which has a downward concave, the methyl esters yield decreases
after a determined ratio. This can be attributed to the balanced transesterification reaction which,
through increasing methanol-to-oil ratio, increases the methyl esters (biodiesel) production (Chuah
et al. 2015a; Kelkar, Gogate, and Pandit 2008; Tamilarasan and Sahadevan 2014). It is worth noting
that such an increase of methyl esters yield is restricted by the increase of methanol-to-oil ratio since
in case this ratio exceeds a particular level, then the purity of the produced biodiesel decreases. The
reason lies in the fact that the increase of methanol in the mixture results in the more increased
dissolution of glycerin and alcohol in biodiesel and affects its purity to some extent. It was found in
another research that the increase of methanol-to-oil ratio from 6:1 to 7:1 results in a decrease of
methyl esters yield (Hingu, Gogate, and Rathod 2010).
Also, Figure (3d) illustrates that the increase of ultrasound power leads to the increase of methyl
esters yield with a constant trend up to 91% level which is the highest conversion percentage.
Considering the significance of P factor (ultrasound power) and the positive mark of its coefficient in
the model, one can demonstrate that this variable is directly related to the methyl esters yield so that
the increase of ultrasound power results in increased biodiesel production (Ji et al. 2006; Stavarache
et al. 2007). The reason for this procedure can be attributed to increased ultrasound stirring per
increased ultrasound power which results in increasing the surface contact between the two formed
phases (methoxide and oil) (Fayyazi et al. 2015; 2018). The increase of surface, in the method where
ultrasound is used individually, results in a decrease of reaction time from 90min to 6min (Fayyazi
et al. 2014). Other studies showed that the increase in ultrasound results in an increase in free fatty
acid conversion due to the aforementioned reasons (Fayyazi, 2015; Samani et al. 2016). In another
experiment, Kumar, Kumar, and Singh (2010) used the ultrasound system for producing biodiesel
from the coconut oil and concluded that the reaction time, using the ultrasound method, is reduced
by 15–40 times compared to the traditional method. Also, the methyl esters yield was obtained by
more than 98% at 6min (Kumar, Kumar, and Singh 2010).

Optimization of independent variables affecting the performance of the combined

hydrodynamic-ultrasonic system
As the last step, concerning the boundary conditions (Table 4), which involves the maximization of the
methyl esters yield and minimization of consumed energy, optimization was performed. The general
objective of the optimization is to obtain the conditions related to the input parameters which involve
the maximum performance. Results of optimization were as follows: 6:1 methanol-to-oil ratio, 60 s
residence time, 1% catalyst percentage, 250 W ultrasound power. Considering the afore-mentioned
values, the methyl esters yield and consumed energy were obtained as 91.35% and 20.52 kJ, respec-
tively. The experiment was replicated in a laboratory in the point suggested by the software. In the
obtained point, the methyl esters yield and the consumed energy were obtained as 91.70 and 21.45 kJ,
respectively, and this is acceptably different from the point obtained from the model. The comparison
of biodiesel production Performance via the transesterification of different feedstocks with methanol in
the ultrasonic and hydrodynamic cavitation reactors mentioned in Table 5.
The main characteristics of WOC methyl esters, including viscosity, density, acid value, flash
point, heating value, iodine value, sulfur content, and cetane number were measured by means of the
ASTM standards (Table 6). All of these characteristics were then compared with EN 14214 biodiesel
standards. The results revealed that some parameters of the biodiesel produced from WOC including
kinematic viscosity, density, acid value, iodine value, and free glycerin fulfilled the acceptable
10 M. FARVARDIN ET AL.

Table 4. Boundary conditions of dependent and independent variables for optimizing the produced biodiesel.
Name Goal Lower Limit Upper Limit
Reaction Time Is in range 30 90

Catalyst concentration Is in range 0.75 1.25

Molar Ratio Is in range 4 8

Ultrasonic Power Is in range 100 400

Yield Maximize 76.5374 91.0503

Energy Minimize 10.65 32.4

Table 5. Comparison of biodiesel production Performance via the transesterification of different feedstocks with methanol in the
ultrasonic and hydrodynamic cavitation reactors.
Catalyst Reaction FAME
Methanol to oil amount time yield
Oil molar ratio Catalyst (wt%) (min) (%) Reference
Ultrasonic Chicken fat 7:1 KOH 1 wt% 9 94.8 (Fayyazi et al. 2015)
Ultrasoinc Pistacia atlantica Desf. 5.5:1 KOH 1 wt% 7.5 92.4 (Samani et al. 2016)
Ultrasonic Celtis australis L. 10.45:1 Chicken bone- 5.7% 32 95.1 (Ansari Samani
derived CaO et al. 2019)
Ultraonic Sunflower 7:1 KOH 0.95 8.5 90.97 (Hosseinzadeh
Samani et al. 2019)
Hydrodynamic Used Frying Oil - KOH - 10 95 (Ghayal, Pandit,
Cavitation and Rathod 2013)
Hydrodynamic Waste cooking 6:1 KOH 1% 15 98.1 (Chuah et al.
Cavitation Oil (Palm Olein) 2015b)

Table 6. Properties of WCO methyl ester in comparison with biodiesel standard (EN 14214) and diesel.
Properties Units EN 14214 WOC methyl ester Diesel Test method
Methyl ester content % (m/m) Min 96.5 95.5 - EN14103
Density at 15°C g/cm3 0.86–0.90 0.89 0.861 ASTM D4052
Kinematic viscosity mm2/s 3.5–5 4.69 2.96 ASTM D445
Acid value mg KOH/g Max 0.50 0.42 0.18 ASTM D664
Iodine value mg I2/100 g Max 120 119.47 - AOAC CD1-25
Flash point °C Min 120 137 48 ASTM D93
Cetane number - Min 51 49 51 ASTM D613
Free Glycerin %mass 0.02 0.019 - ASTMD6584
Total Glycerin %mass 0.24 0.23 - ASTMD6584

condition according to the EN 14214 standard. Therefore, transesterified WOC could be a potential
alternative to petrodiesel. Hosseinzadeh Samani et al. (2015) reported that Viscosity plays a major
role in fuel injection, fuel mixture formation, and combustion process. The inappropriate mixing of
 ENERGY SOURCES, PART A: RECOVERY, UTILIZATION, AND ENVIRONMENTAL EFFECTS 11

fuel with air may cause a misfire. The viscosity of each fuel depends on its chemical structure.
Viscosity increases with increasing the length of the hydrocarbon chain and decreases with increas-
ing the number of double bonds in the hydrocarbon chains. Also, the viscosity is directly propor-
tional to the heating value of fuel (Samani et al. 2016). According to empirical relationships, the
viscosity of the fuel should be approximately equal to 4.2 mm2/s, which is expected in 100%
conversion state of fatty acids to methyl esters. However, the methyl esters yield in the optimal
conditions of the research was equal to 95.5%. The 4.5% unconverted fatty acid may be the major
reason for the obtained viscosity value. On the other hand, the experimentally obtained value could
be associated with experimental errors (human operator error) which could, in turn, cause
a difference between the empirical and experimental value. All biodiesel fuels are denser and less
compressible than the diesel fuel irrespective of feedstock type (Alptekin and Canakci 2008; Ghazali
et al. 2015). The molecular weight of biodiesel is one of the factors that contribute to increasing
biodiesel density(Alptekin and Canakci 2008).

Comparison of conventional methods and ultrasonic system for biodiesel production

The study of biodiesel production using the conventional method (mechanical stirrer, 600 rpm,
60°C) revealed that the greatest biodiesel conversion can be obtained at a reaction time of
70–90 min. In the optimal condition, the time of biodiesel production by the combined method
(at a methanol-to-oil ratio, catalyst concentration, ultrasonic power and reaction time of 6:1, 1%,
250 W and 60 s, respectively) was 90 times lower than that by a conventional method (Figure 4).
Transesterification reactions include the reaction between oil and alcohol in the presence of a catalyst.
Oil and methyl alcohol are incompatible liquids and when they react in one tank, two separate layers are
formed. Transesterification reactions commercially require continuous mechanical stirring over a long
period of time, because the reaction between alcohol and oil can only be carried out at the point of
contact between the two liquids (on a molecular scale). When this mixture is entered to shock waves
reactor, rotational rotor and cavity of rotor cause cavitation at the contact poin. As a result, an emulsion
of oil and alcohol is formed that provides a wide surface for reactions. It has been observed that the
reaction time is significantly reduced (Chand et al. 2010). Abbaszadeh-Mayvan reported similar results
that confirm the data of present research (Abbaszadeh-Mayvan et al. 2018). In other words, the
hydrodynamic method decreased the time of reaction to obtain the desired biodiesel conversion.

Ultrasonic-Hydrodynamic Conventional method

100

80
Conversion (%)

60

40

20

0
0 20 40 60 80 100
Reaction Time (min)

Figure 4. Comparison of biodiesel conversion rates between ultrasonic-hydrodynamic method (at a methanol-to-oil ratio, catalyst
concentration, ultrasonic power and reaction time of 6:1, 1%, 250 W and 60 s, respectively) and the conventional stirring method
(600 rpm, 60°C).
12 M. FARVARDIN ET AL.

Conclusion
Biodiesel was produced from the waste oil by a combined hydrodynamic reactor-ultrasonic cavita-
tion device. To attain desirable production in terms of the maximum the methyl esters yield and
minimum cost of fuel production, the response surface method was used. Findings of the study
indicated that in the case of biodiesel production from the waste oil, the methyl esters yield follows
an increasing trend, but after the time passing, i.e. up to 90 s, the methyl esters yield decreases. The
increase of catalyst percentage by 1% results in an increase of the methyl esters yield, and up to
1.25% catalyst, the methyl esters yield decreases by 7%. The increase of methanol-to-oil ratio up to 6
leads to the increase of the methyl esters yield, and up to methanol-to-oil ratio 8, it follows
a decreasing trend with a slight slope. Also, the increase of ultrasound power results in an increase
of the methyl esters yield with a constant ratio. The optimal conditions of the present study are as
follows: at the 60 s time, 1% catalyst concentration, 6:1 alcohol to oil methanol-to-oil ratio, and
250 W power, the methyl esters yield and the consumed energy were obtained as 90.45% and
21.52 kJ, respectively. Therefore, the suggested method is suitable for biodiesel production as the
methyl esters yield and energy consumption.

Acknowledgments
The authors are grateful to the Research Council of Shahrekord University is thankfully acknowledged for their
financial support for conducting this study (grant No:96GRN1M1796). Also, the authors express their thankful regards
for Tarbiat Modares University (http://www.modares.ac.ir) for financial supports given under IG/39705 grant for
Renewable Energies of Modares research group.

Funding
This work was supported by the Shahrekord University [96GRN1M1796];Tarbiat Modares University [IG/39705].

Notes on contributors
Mahrokh Farvardin is M.Sc students of agricultural mechanization engineering. She has worked on intensification and
find the new resource of biodiesel production. The present research related to her thesis in M.Sc grade.
Bahram Hosseinzadeh Samani is associate professor of mechanical engineering of biosystem in Shahrekord
University, Iran. He was born in December of 1983. His research interests include biodiesel, biogas, and applied
novel technology in the agricultural process.

Sajad Rostami is associate professor of mechanical engineering of biosystem in Shahrekord University, Iran. His
research interests include renewable energy and design and manufacturing of machine that related to agricultural
operations.

Ahmad Abbaszadeh-Mayvan is assistance professor of Biosystems Engineering Department, Gorgan University of

Agricultural Sciences and Natural Resources, Gorgan, Iran. His research interests include renewable energy and design
and manufacturing of machine-related to agricultural operations.
Gholamhassan Najafi is associate professor of mechanical engineering of biosystem in Tarbiat Modares University,
Iran. His research interests are renewable energies and internal combustion engines (Scopus h-index = 30).

Ebrahim Fayyazi is a researcher at the Renewable Energies Research Institute, Tarbiat Modares University (TMU-
RERI), Tehran, Iran. He obtained his Ph.D. in mechanical and biosystems engineering from TMU in 2018. His main
research area is biodiesel production using intensification methods.

ORCID
Mahrokh Farvardin http://orcid.org/0000-0002-7946-3926
Bahram Hosseinzadeh Samani http://orcid.org/0000-0002-8563-7080
 ENERGY SOURCES, PART A: RECOVERY, UTILIZATION, AND ENVIRONMENTAL EFFECTS 13

Sajad Rostami http://orcid.org/0000-0002-0375-0558

Ahmad Abbaszadeh-Mayvan http://orcid.org/0000-0002-6917-9833
Gholamhassan Najafi http://orcid.org/0000-0003-3125-3804
Ebrahim Fayyazi http://orcid.org/0000-0002-2935-2291

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