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The influence of using sonicator type to produce alcohol in the glycerol degradation

process
Ruslan Kalla, S. Sumarno, and M. Mahfud.

Citation: AIP Conference Proceedings 1840, 040004 (2017); doi: 10.1063/1.4982271


View online: http://dx.doi.org/10.1063/1.4982271
View Table of Contents: http://aip.scitation.org/toc/apc/1840/1
Published by the American Institute of Physics

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The Influence Of Using Sonicator Type To Produce Alcohol
In The Glycerol Degradation Process

Ruslan Kalla1*, S. Sumarno2, M. Mahfud3.


1
Chemical Engineering Department, Faculty of Industrial Technology, Muslim University of Indonesia, Makassar
(Graduate Student Chemical Engineering Department, Faculty of Industrial Technology, Sepuluh Nopember
Institute of Technology, Surabaya)
2,3
Chemical Engineering Department, Faculty of Industrial Technology, Sepuluh Nopember Institute of Technology,
Surabaya, Indonesia)
*E-mail : ruslan_kalla@yahoo.com.

Abstract The last few years the energy crisis happens everywhere, not least in Indonesia. One reason is the need for fossil
energy is increasing with the increasing population, in addition to the depletion of oil reserves on the Earth Indonesia.
Therefore it takes a plant-based alternative energy, one of which is biodiesel. The transesterification process will produce
primary products such as methyl ester and byproducts / waste in the form of about 10-15 % glycerol so that glycerol is quite
abundant. This research aims to study the effect of the sonicator type (vibrating horn and cleaning bath) as well as the effect
of -Al2O3 catalyst on the degradation of glycerol. The production process was conducted in a batch reactor equipped
with an ultrasonic wave generator. Operating conditions of this study was the atmospheric pressure with mass ratio of
glycerol water 1:10. The research variables were sonication temperature of 30 and 40 C, sonication time of 10, 30, 50, 70
and 90 minutes with and without the catalyst. Products of degradation were analyzed by Gas Chromatography (GC). The
results showed that, the products of degradation product (methanol and allyl alcohol) using a sonicator vibrating horn type
were greater compared to using cleaning bath type sonicator. The glycerol conversion was 63.21 % at sonication time of 90
minutes, a temperature of 40 C using - Al2O3 catalyst. While the greatest product yield was 18.17 % methanol at
sonication time of 90 minutes, a temperature of 40 C with the use of vibrating horn sonicator type, with the addition of -
Al2O3 catalyst.

Keywords : Glycerol, degradation, vibrating horn, cleaning bath, alcohol

INTRODUCTION
Glycerol as the main raw material in this study can be obtained from a variety of ways, one of which is a byproduct
of biodiesel production. Glycerol is a chemical that has the potential to be converted into fuels such as methanol,
ethanol (Buhler et al. 2002), and hydrogen (Adhikari et al. 2007) and compounds that have added value such as
acrolein, acetaldehyde, formaldehyde, and allyl alcohol ( May et al. 2010).
The degradation process of glycerol has been done by previous researchers as steam reforming [Adhikari et
al. 2007, Byrd et al. 2002)], hydrothermal [Buhler et al. 2002, Zhao et al. 2013], the catalytic hydrogenation [Lehr et
al. 2007], the catalytic dehydration [Omata et al. 2012], Pyrolysis [Buhler et al. 2002, Vallyapan et al. 2008],
hydrogenolysis [Gandarias et al. 2011, Guo et al. 2009]. However, these processes still require operating conditions at
high temperature and pressure thus requiring a high operating cost.
There is an alternative process to degrade glycerol that is degradable by using ultrasonic waves, known as
sonication process. The sonication process can be operated at lower tem- peratures and be performed without catalysts.
In this study, degradation of glycerol with and without catalyst was investigated.

International Seminar on Fundamental and Application of Chemical Engineering 2016 (ISFAChE 2016)
AIP Conf. Proc. 1840, 040004-1040004-6; doi: 10.1063/1.4982271
Published by AIP Publishing. 978-0-7354-1510-2/$30.00

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Sonication process is a process that uses ultrasonic waves with frequencies between 20-100 kHz. The process is
easily applied to a variety of destinations such as degradation and modification reactions [Clements, 1995]. One of the
benefits of ultrasonic process is to accelerate the reaction process [Kudiloke et al. 2006, Cameroon 2006].
The catalyst employed in the degradation process accelerates the chemical reaction. The catalyst used as follows:
Cu/SiO2 [Huang et al. 2011], Cu/MgO [Yuan et al. 2010], Al2O3 [Cifti et al. 2012], HZSM [Gu et al. 2012], -Al2O3
[Pathak et al. 2009, Kalla et al. 2015], CuSO4 [Yuniati 2012], H3PO4 [Qadariyah et al. 2011, Kalla et al. 2016]
This research aims to study the effect of the type of sonicator (vibrating horn and cleaning bath) as well as the
effect of -Al2O3 catalyst on the degradation of glycerol.

METHODOLOGY / EXPERIMENTAL

Material

Glycerol used in this work, was obtained from BRATACO Chemical Co. Ltd. with a purity of 91 % (w/w) and the
-Al2O3 catalyst was purchased from MERCK and the pure water was used as solvent.

Apparatus
Equipment was used to this study with sonication process using vibrating horn sonicator
types that are arranged as in Figure 1. The reactor used was a batch reactor type made of stainless steel type 316 SS
Swagelok production. Dimensions of the reactor is 8.5 cm high, 6.5 cm in outside diameter, inside diameter 5.5 cm, 1
cm thick with a volume of 400 ml. The reactor was equipped with a condenser used to minimize the loss of solution
due to evaporation and also with termocouple of type K TC4S to know the temperature inside reactors. Besides, it also
used a water bath to keep the temperature of the reactor as well as data taker for is recording temperature changes
during surgery. Vibrating horn that was used was a High Intensity Ultrasonic Processor VCX 500 Sonics and
Materials Inc., USA (500 W, 20 kHz) equipped with a probe transducer Titanium Alloy. Piezoelectric converters made
of lead crystal zirconat titanate. The tip of the probe diameter of 1.3 cm and submerged about 1 cm from the bottom of
the reactor.
While the specifications of the equipment used to experiment with sonication process using a cleaning bath sonicator
types are assembled as shown in Figure 2. The reactor used was a reactor made of glass (three neck flask) with a
volume of 500 ml. The reactor was equipped with a condenser used to minimize loss of solution due to evaporation
and also with termocouple dilegkapi type K type TC4S to know the temperature inside reactors. sonicator bath Type
used was brand KRISBOW Ultrasonic Cleaner KW 1801033 models with specifications are voltage 240 V
/ 50 Hz, 100 W power, 20 and 40 KHz frequency, capacity of 2.8 L, tank dimensions of 235 x 135 x 100 mm and
outer dimensions of 265 x 165 x 240 mm.

Experimental Procedure
Before being employed, the -Al2O3 catalyst was activated through calcination at temperature of 550 C for 5 h
then analyzed by XRD. The analysis performed was to identify the crystalline phases in the material.
Degradation was carried out by inserting glycerol-water mixture into reactor with a mass ratio of 1:10. The three
percent catalyst of glycerol (w/w) was added into solution, and the sonication equipment was run. Figure 1 shows the
equipment design used in this work (vibrating horn type). The degradation process was started when the sound wave
was generated. The process stopped when time attained as previously set. Operating conditions were atmospheric
pressure and glycerol-water mass ratio was 1:10. Research variables were as follows: the temperatures of sonication
were 30 and 40 oC, sonication times were 10, 30, 50, 70 and 90 min for catalyst treatment and those were
compared to without catalyst. Products obtained were analyzed using GC with Agilent column type 19091Z-213, with
operating conditions were as follows: maximum column temperature 325C, the maximum oven temperature of 325
C, a temperature of 300 oC front detector, FID detector type (front) and TCD (rear), feed rate of 1.6 ml/min, an air
flow of 300 ml / min, the hydrogen rate of 30 ml/min, the carrier gas is helium, the run time of 7.5 minutes.

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Figure 1. Experimental apparatus for vibrating horn sonicator type. Descriptions: (1). Ultrasonic Power; (2). Probe Sonicator; (3).
Reactor; (4). Condensor; (5). Water bath; (6). Chiller; (7). Recorder Data; (8). Thermocouple

To process using the cleaning bath sonicator type was carried out by inserting glycerol- water mixture into
reactor with a mass ratio of 1:10. The three percent catalyst of glycerol (w/w) was added into solution, and the
sonication equipment was run. Figure 2 shows the equipment design used in this work (vibrating horn type). The
degradation process was started when the sound wave was generated. The process stopped when time attained as
previously set. Operating conditions were atmospheric pressure and glycerol-water mass ratio was 1:10. Research
variables were as follows: the temperatures of sonication were 30 and 40 oC, sonication times were 10, 30, 50,
70 and 90 min for catalyst treatment and those were compared to without catalyst. Products obtained were analyzed
using GC as the process by using a vibrating horn sonicator type.

Figure 2. Experimental apparatus for cleaning bath sonicator type. Descriptions: (1). Pumpkin pedestal plate three neck; (2).
Materials and solvents; (3). Sonicators; (4). Sonicator Regullator; (5). Indicator of sonicator; (6). Condensor; (7). The temperature
indicator

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3. RESULTS AND DISCUSSION
Table 1. The data of angles appearing of catalyst and compared to those of standard.

-Al2O3 (JCPDS
Position[2]
standard)
37.19 37.6
38.90 39.49
43.57 45.79
45.51 48.93

80
Vibrating horn type
70
Cleaning bath type
60
Conversion (%)

50
40
30
20
10
0
0 20 40 60 80 100
Sonikation time (minute)

o
Figure 3. The effect of sonicator type against glycerol conversion at 40 C with alumina catalyst

20

Vibrating horn type


Yield of Methanol (%)

15 Cleaning bath type

10

0
0 20 40 60 80 100
Sonikation time (minute)

Figure 4. The effect of sonicator type against yield of methanol at 40 oC with alumina catalyst

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20

Vibrating horn type

Yield of allyl alcohol (%)


15 Cleaning bath type

10

0
0 20 40 60 80 100
Sonikation time (minute)

Figure 5. The effect of sonicator type against yield of allyl alcohol at 40 oC with alumina catalyst
Table 1 is the data of angles appearing of catalyst and compared to those of standard. The angles of peaks of
catalyst (-Al2O3) after calcination were relatively similar to those of JCPDS standard. The catalyst, which has been
prepared, showed the clear peaks in XRD pattern at 37.19 o, 38.90o, 43.57o and 45.51o. Those values were close to
o
JCPDS standard, 37.60o, 39.49o, 45.79o and 48.93 . It was indicative that the -Al2O3 catalyst has been successful
activated performing a calcination.
The physical properties of the catalyst, the surface area and pore diameter, were also characterized using BET
method. The BET analy-sis found that activated catalyst has a surface area of 123.004 m /g with a pore diameter of
6.072 nm. The surface area on the catalyst was high category (100-500 m /g) and the pore di-ameter was ranged from
2-10 nm, which was mesoporous (medium).
The influence of sonication time on the conversion of glycerol with using the -Al2O3 catalysts is shown in Figure
3. The figure shows that, the conversion of glycerol increased as sonication time inclined. The significant improvement
of conversion was occurred at the range 10 to 90 min. things are going well in the use of to two sonicator types.
The increase in conversion was due to the effect of ultrasonic wave intensity. The longer period of sonication
occurred, the longer proc-ess of cavitation took place. The cavitation influence on the physical and chemical
conditions, was quite extreme in the mixture. The reactants destruction was caused by the bursting of sound waves
during cavitation, which reduced the concentration of glycerol and then increased the conversion until a certain time
[Cravotto and Cintas, 2005]. It was found that sonication time is very influential on the cavitation, so that conversion
significantly increased as previously reported [Buhler et al. 2002, Yuan et al. 2010, Williams 1983]. The use of
vibrating horn sonicator type, the conversion of glycerol increased until 50 min, and then stabilized until 90 min.
Influence of sonication time on the yield of product is shown in Figure 4 and 5. The yield of each product either
methanol or allyl alcohol increased as sonication time inclined. Yield of allyl alcohol (6.2 %) obtained was relatively
small compared to that of methanol (18.17 %) lower due to product allyl alcohol caused by allyl alcohol products can
be obtained at high temperature and pressure conditions. Another case with methanol, this product can be obtained at a
temperature and a lower pressure so that the yield of methanol is greater than the yield of allyl alcohol (Buhler et al.
2002)
CONCLUSION
From the results of research conducted the conclusion as follows:
1. Ultrasonic wave radiation for glycerol degradation process can be used to produce other compounds
such as acrolein and others.
2. The biggest conversion was obtained by the use of catalysts -Al2O3 is 63.21 % in the sonication time of 90
minutes and a temperature of 40 oC with the use of vibrating horn sonicator type.
3. The highest yield obtained was 18.17 % methanol with the use of catalysts -Al2O3 at 90 min. sonication
time and temperature 40 oC with the use of vibrating horn sonicator type.

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