INDONESIAN SCHOLARS JOURNAL Paper Number (Will be replaced with volume and paper number if the

manuscript is accepted)

Implementation of Ultrasonic Microbubbles
Method in Biodiesel Trans-esterification Process of
a Vegetables Oil Residue
Agung Cahyono, Hakim Al Kausar, Dwi Wulandari, Bambang Susilo, Dimas Firmanda Al Riza
Departement of Agricultural of Engineering, Faculty of Agricultural Technology, University of Brawijaya
Jl. Veteran Malang 65145

Corresponding author : 115100213111008@email.ub.ac.id
Abstract. Biodiesel is one of choices of renewable energy that can be made by using vegetable or animal oils. In this study a
residue of frying vegetable oil is used as the main ingredient. In a conventional batch trans-esterification process a mechanical
stirrer is commonly used and it takes a considerable amount of time between 30 minutes to 2 hours for the reaction to be
completed. The biodiesel conversion yield by conventional process is approximately 96%. Trans-esterification reaction kinetics
must be considered to obtain an efficient process and better yield. The use of ultrasonic with horn type transducer (Braun Sonic
2000) in the process of trans-esterification reaction showed higher specific energy and can reduce specific energy in biodiesel
processing than a conventional method and also shorten the processing time. The experiments were performed using a catalyst
(KOH) and methanol with a molar ratio of (1:6) with a volume of 125 mL and carried out with process time between 3-25
minutes. The results show the highest biodiesel yield is 100% with process time of 3 minutes. Other measured parameters met
the biodiesel standard with a great Flash Point of 107
o
C, density of 0.871 gram/mL, 9381.221 calorific value (calories/gram), the
viscosity of 6 cP, and the processing time of 7 minutes obtained biodiesel conversion yield of 98.4% at 108
o
C Flash Point,
Density 0.871 gram/mL, 9329.890 calorific value (calories/gram), and the viscosity of 6 cP.
Keywords: biodiesel, trans-esterification, ultrasonic, used cooking oil
A. INTRODUCTION
Numerous attempts have been done to decrease the use of
fossil fuels which its supply will be estimated run out in the
next 25 years. These attempts should be done considering the
gas emissions of this fuel such as CO
2
, PbO, CO, SO
2
, carbon
and hydrocarbon which pollute the environment. Biodiesel is
one of the alternative fuel for the transportations in which its
produce less emissions (CO, HC, particle and dust)
environmentally friendly and recyclable [1].
The serious increasing price of petroleum and the
environmental effect has become the background for searching
some alternative diesel fuels from renewable resources called
biodiesel [2,3]. Biodiesel is a renewable alternative fuel
produced through trans-esterification or esterification of fatty
acids from plant oils [4].
The use of Biodiesel which is mostly made from vegetable
or animal oils is commonly contrasted to the foodstuffs.
Cooking oil is leftover oil that is able to be utilized as the
inexpensive and sustainable biodiesel materials. The aim of
using this oil is utilizing waste and decreasing the carcinogenic
impact leading to cancer. The cooking oil consumption with
deep frying in Indonesia reaches 182 thousand ton along with
the assumption that the half of this oil is wasted. Considering
these data, it is assumed that the wasted oil reaches 91
thousand ton. Hence, the use of these materials must bring the
higher economic value than the other biodiesel materials [5].
Oil-made Biodiesel production generally uses the
mechanic stirrer. It has so many drawbacks such as: consume a
large number of energy, numerous catalyst, lack of yield and
time-consuming process. Therefore, it necessarily needs the
effective method to solve these problems which is horn-jolted
ultrasonic cavitation method. This method is used for it has
several advantages such as: less time-consuming process,
99.99% productivity, small energy input, less number of
catalyst and maximum generated product [6].
B. IMPORTANT REQUIREMENTS
1. Materials
The used materials in this study consist of wasted cooking
oil, KOH (base catalyst), methanol ( 90% degree) while the
used aids consist of Braun Sonic 2000, measure glass (1000
ml, 500 ml, 200 ml), thermometer, centrifuge, Hot Plate/
Stirrer HP220, Timer, loaded (Volume 1000 ml, 1500 ml),
Oscilloscope.
2. Methods
The applied method in this study is random design along
with the analysis of time reaction of trans-esterification by
head-jolted ultrasonic wave (Braun Sonic 2000) toward final
biodiesel product after the trans-esterification process. The
samples used in this study are 12 samples and the ultrasonic
INDONESIAN SCHOLARS JOURNAL Paper Number (Will be replaced with volume and paper number if the
manuscript is accepted)

frequency used is stable on the Braun Sonic 2000 which is on
the high frequency (29.53 kHz).
3. Experimental Design
The purpose of testing it is time to get the range of steady
process of trans-esterification based on feculence glycerol
formed. A mixture of oil and methoxide with a volume of 125
ml processed by ultrasonic waves horns a trill. The ratio of the
molar oil and methanol made 1:6. The catalyst used is a
concentration of 10 gram KOH per liter of the oil (equivalent
0.216 mole KOH/liters oil) continued with the use of a catalyst
1% or 0.9 grams. After the process of trans-esterification
lasting the next process neutralized with H
2
SO
4
and
centrifugation in 5000 rpm for 3 minutes to see the volume of
feculence glycerol.
4. Calculation of Specific Energy
Calculation of specific energy obtained based on
calculations energy obtained based on data specifications of
instrument that stated in instrument Braun Sonic 2000.
Immensity energy needs specific in processing palm oil
biodiesel be obtained from equation 1.






5. Percentage of the Glycerol
Percentage of the glycerol obtained by volume glycerol
acquired divided by volume material. Immensity percentage of
volume glycerol obtained from equation 2.




C. RESULTS AND DISCUSSION
1. The Effect of Time Process to the Value of Methyl
Ester Cinematic Viscosity
The data of viscosity testimony in this study are the
testimony result by using S-flow 3000v automatic viscosity
system. This aid uses the set of mm
2
/s or known as centipoise
(cP). The results of this test can be seen through the Figure 1.





Fig 1. The cinematic viscosity correlation graphic toward time

Figure 1 shows that the large of cinematic vescosity toward
needed time of the transesterification process is not linier. It
tends to up and down especially at the particular reaction time
such as 9 minutes, 11 minutes, 13 minutes and 15 minutes.
While the transesterification reaction over 15 minutes shows
the stable increasing cinematic viscosity which is
approximately on the 7 mm
2
/s. generally, it can be recognized
that the longer time of trans-esterification process results the
higher value of biodiesel viscosity toward these following
times: 9,13,17,19,21,23 and 25 minutes in which these times
are out of the Indonesian viscosity standard. It also happens in
the research Fatmawati et al [7] that the large influence of
cinematic viscosity toward the duration of trans-esterification
reaction in creating biodiesel tends to increase due to the
active of carbon bound resulting the decrease of biodiesel
temperature. It also influences the fuel pump function.
Consequently, it can be said that the cinematic viscosity value
of biodiesel which is related to the SNI is less than 6 mm
2
/s,
which is under reaction of 3, 5, 7, and 11 minutes.
2. The Effect of Time Process to the Methyl Ester
Yield
The higher value of the yield means the more growing
number of the biodiesel percentage produced during the
ongoing trans-esterification process. The yield value can be
measured by dividing the final oils weight by the former oil
weight and then times by 100%. Therefore, the yield is
commonly expressed in the form of percentage (%) and the
maximum yield of biodiesel is 100%. The yield of this study
can be seen through the Table 1.
Table 1. Biodiesel yield in the difference time variations
Time (minutes) Yield (%)
3 100
5 94,4
7 98,4
9 96,8
11 96,8
13 95,2
15 96
17 95,2
19 95,2
21 98,4
23 92
25 95,2
According to the Table 1, it can be seen that the biggest
yield is gained in the 3 minutes trans-esterification reaction
with 100% of yield value. It shows that 100% of the materials
can be converted into biodiesel. The trans-esterification
biodiesel during 3 minutes can produce 125 ml biodiesel by
using the former 125 ml cooking oil. While the smallest yield
value is gained on the 23 minutes trans-esterification process
which is 92%. The holistic biodiesel yield percentage tends to
be unstable. However, the decrease tendency of biodiesel yield
in this study is mostly caused by the decrease of methanol by
result of increasing temperature of the ultrasonic radiation.
This also happens in the research Zuliana et al [8] stating that
(2)
(1)
5.4
5.6
5.8
6
6.2
6.4
6.6
6.8
7
7.2
3 5 7 9 11 13 15 17 19 21 23 25
V
i
s
c
o
s
i
t
y


(
m
m
2
/
s
)

Time (minutes)
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manuscript is accepted)

0
20
40
60
80
100
120
3 5 7 9 11 13 15 17 19 21 23 25
methyl ester yield tends to decrease due to the trans-
esterification reaction which is categorized as the reversible
reaction. Therefore, the increasing time of trans-esterification
reaction may cause the reverse reaction as well as the ethanol
evaporation due to the increasing temperature. It eventually
results the decreasing value of biodiesel yield.
3. The Effect of Time Process to the Flash Point of
Methyl Ester
The result of flash point of methyl ester (biodiesel) can be
seen through the Figure 2.




Fig 2. Flash point of methyl ester toward the trans-esterification time
Test result in figure 2 shows that the flash point of
produced methyl ester mostly meets SNI 04-7182-2006 in
which the minimum value of flash point for the biodiesel is
100
o
C. The lowest flash points gained in the low frequency
treatment with 23 minutes of trans-esterification process which
is 44 C. While for the highest bur point is 114 C in 15
minutes trans-esterification treatment. According Setiawati et
al [9] the flash point primarily links to the safety during the
saving and handling process, in which the flash point shows
the ability whether or not it can be burned and evaporated
(volatility). Thereby, flash point value of biodiesel which is
produced above 100
o
C has been feasible to be used.
4. Time Influence of Trans-esterification Toward the
Heat Value of Methyl Ester
Heat value shows the bigger energy amount which is freed
by the fuel through the perfect combusting reaction per set of
mass or fuel volume. From the biodiesel manufacture through
the use of this cooking oil, it is gained the heat value of
biodiesel as seen in the Figure 3.





According to the Figure 3 it can be seen that the highest
heat value is gained in 19 minutes of trans-esterification
reaction with the heat value is over 10,000 cal/gram and the
lowest heat value is gained in 9 minutes which is 8.000
cal/gram. According to SNI the heat value of biodiesel should
be more than 27.65 Btu/lb. The inconstant increase of heat
value shows that the time does not significantly influences
toward the degree of heat value of produced biodiesel. The
insignificance of this matter also happens in the research
conducted by Fatmawati et al [7] which states that the heat
value of biodiesel tends to be stable.
5. Time Influence of Trans-esterification Toward the
Methyl Ester Density Value
The density or substance mass in biodiesel has the
significant role toward its cinematic viscosity since this
density value is directly proportional to its cinematic viscosity
value. In biodiesel, the density value shows the number of
pollutant substances, such as soap and glycerol as the result of
soaping reaction, unconverted fat which later becomes ester,
water, wasted hydroxide sodium, or even unreacted waste
methanol [9]. The result of methyl ester density toward the
time influence can be seen through Figure 4.





Fig 4. Density value of methyl ester toward the trans-esterification
process
Figure 4 shows that the density value of methyl ester
produced form the trans-esterification reaction toward the
cooking oil mostly in the number of 0.869-0.872 gr/ml. These
numbers holistically meets the criteria of biodiesel based on
SNI which is 0.85-0.9 gr/ml. The highest value of methyl ester
density is during 9, 11, 13, 15, 17, 21 and 23 minutes of trans-
esterification process which is 0.872 g/ml while for the lowest
value is in 25 minutes of trans-esterification process which is
0.870 gr/ml. based on the picture 4, it can be seen that the
value of methyl ester density tends to be unstable which is
marked by up and down the density value in each reaction
time. This result goes in a line with the research conducted by
Arfika et al [10] in which the methyl ester density value is
significantly increased but then fall back as the increase of the
F
l
a
s
h

P
o
i
n
t

(
o
C
)

Time (minutes)
0
2000
4000
6000
8000
10000
12000
3 5 7 9 11 13 15 17 19 21 23 25
Time (minutes)
H
e
a
t

V
a
l
u
e

(
c
a
l
/
g
r
a
m
)

Fig 3. Heat value of methyl ester toward the trans-esterification
process

0.869
0.8695
0.87
0.8705
0.871
0.8715
0.872
0.8725
3 5 7 9 11 13 15 17 19 21 23 25
Time (minutes)
D
e
n
s
i
t
y

(
g
r
a
m
/
m
l
)

INDONESIAN SCHOLARS JOURNAL Paper Number (Will be replaced with volume and paper number if the
manuscript is accepted)

trans-esterification time in the process of biodiesel
manufacture.
6. Energy Calculation
On the research of Sholikah et al [11] specific energy
needs, biodiesel processing at optimal conditions with
ultrasonic wave of 576 kJ/liters. According to Susilo [12];
using mechanical energy specific stirring to the specifications
that engine as follows: Heater 1kwatt, the process of 30
minutes, TG conversion to E: 96%, and the Capacity 1,5 liters
of every process. The energy needs of each liter of biodiesel,
Trans-esterification products:




It shows that the use of ultrasonic wave trans-esterification
need to the process of energy specific stirrer lower than the use
of mechanical.
D. CONCLUSION
Reference used cooking oil can be used as a potential
materials for biodiesel manufacture. The process of making
biodiesel from wasted cooking oil may use method which
applies the horn-jolted ultrasonic as trans-esterification with
1% of KOH catalyst and 90% methanol concentration. Based
on the results of this study, it was found that biodiesel has
complied with SNI 04-7182-2006 in which the best results are
in the trans-esterification reaction for 3 minutes which resulted
in 100% yield, 6 cP of cinematic viscosity, 0.871 g/ml od
density, 107
o
C of flash point and 99831.211 cal/g of the heat
value at a frequency of 29.53 kHz ultrasonic waves.
ACKNOWLEDGEMENT
We gratefully to Dr. Ir. Bambang Susilo, M.Sc.Agr and
Dimas Firmanda Al Riza, ST, M.Sc., as the supervisor who
has helped us in the preparation of the experiment, in the form
of guidance, discussion, referrals, and prayer. And also
acknowledge to all those who have helped both moral support
and prayers which the writer cannot mention here. This paper
will be more complete with head vice and constructive
criticism to improve the preparation of subsequent papers.
Finally, the author hopes that the preparation of this paper can
be useful.
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