International Conference On Chemical Sciences (ICCS-2007)

Innovation In Chemical Sciences For Better Life

Yogyakarta-Indonesia, 24-26 May, 2007
COMP/41-5

PREDICTING THE AZEOTROPIC OF CITRONELLAL ENRICHMENT USING

PROCESS SIMULATOR

Joddy Arya Laksmono*, Egi Agustian, Indri Badria Adilina

Process Technology and Synthesis of Essential Oil Research Group
Research Center for Chemistry – Indonesian Institute of Sciences
Kawasan PUSPIPTEK Serpong, Tangerang, Banten, Indonesia 15314

ABSTRACT

In the laboratory, we have found three main components of citronella oil, citronellal, citronellol, and geraniol.
Citronellal enrichment is generally obtained by fractionation unit. Those three components are usually obtained in
azeotropic system. In the preliminary study, we have found that citronellal in the distillate with concentration of more
than 90% was mixed with other components, mainly citronellol and geraniol. Gas chromatography was used for
analysis of citronellal component. In this study, we have predicted the azeotropic system in fractionation unit for
citronellal enrichment as an illustration using ChemCAD process simulator. The result of citronellal enrichment
simulation will be discussed in this paper.

Keywords: Citronellal enrichment, azeotropic, simulation, ChemCAD.

INTRODUCTION Fractionation distillation is separation of liquid

Citronella oil is one of the most interesting essential
oil, mainly it will be used in any industry of flavor and
fragrance’s, cosmetics, pharmaceutical, food, and so on.
Essential oil, usually has a vary components in their
mixture. Furthermore, separation and purification of the
essential oil mixtures will be difficult to separate.
Physically, many components in the essential oil have
same boiling point and chemical structured, or have a
boiling point near to the other components. We used
original Java citronella oil (Cymbopogon winterianus
Jowitt) as a raw material for separation simulation in the
laboratory. The smell of oil of citronella repels blood-
feeding mosquitoes, ticks, and fleas. As a non-toxic
substance, many people prefer citronella to other
chemical repellants such as DEET (N, N-diethyl-meta-
toluamide). Citronella oil appears in many products
designed to protect humans, pets, and open-air spaces
from the public health risks posed by mosquitoes and
ticks. A concerned person could use sprits on their
clothing, lotion or soap on their skin, treated collars on
their pets, and candles or pellet bags surrounding their
picnic [1].
Main component of citronella oil are citronellal,
citronellol, and geraniol. The physical properties of their
components shown that, citronella has a relative higher
different boiling point toward citronellol and geraniol.
Kindly this component has a 20 oC different boiling
temperature due to citronellol dan geraniol. Furthermore,
citronellol and geraniol has a relative nearly in their
boiling point, and then this both components are already
in mixture after separated from citronellal. The mixtures
of citronellol and geraniol could be named as rhodinol [2].
mixture according to main compound vapor pressure
difference. Fractionation is process series evaporation
flash stages, which is arranged in series of vapor and
liquid, due to reversible flow from every stage to next
stage. In this condition, liquid will flow to the next
bottom stage and vapor will go to the next stage above.
In fractionation distillation system was completed with
reflux unit to increase fraction quality [3].
The Vapor-Liquid Equilibrium (VLE) is an
important role for design of fractionation unit. In this
paper, we are determining the VLE for separation of
citronella oil to produce citronellal, citronellol, and
geraniol. Design of columns for separating azeotropic
systems includes the analysis of feasible separations of
a mixture of a given composition xf,I, that is, the
determination of the feasible compositions of overhead
and bottom products. The answer to this key question
of rectification theory depends on three factors: the
features of the field of vapor–liquid equilibrium ratios,
the mode of separation which is liquid essential oil, and
the scheme of the column (specifically, whether the
column has one feed) [4,5,6].
In this work, we are aim the equilibrium data for
separation of citronella oil using batch vacuum
fractionation at low pressure, and also a dimension
data for the column, such as outside and inside
diameter, height, theoretical tray number, and so on.
The data are consisted of Txy, xy graphics. The
equilibrium data was assessed using ChemCAD
simulator. We was simulated the separation process in
two step dynamics condition using Cubic State
Equation.

* Corresponding author. Tel: +62-21-7560929, Fax : +62-21-

7560549; Email address : joddy_arya_laksmono@yahoo.com
2 Proceeding of ICCS 2007, Yogyakarta-Indonesia, 24-25 May 2007

EXPERIMENTAL SECTION to produced three main component was used a batch

vacuum fractionator in the vacuum pressure condition
Materials 40 – 80 mbar and temperature was 120 oC – 150 oC.
Citronella oil which is original Java essential oil was We assumed that the separation has a binary system
supplied from local commercial home industry with citronellal-rhodinol. This process was determined the
concentrations of citronellal 32.15%, citronellol 12.95%, physical properties of citronellal, citronellol, and
and geraniol 20.54%. The physical properties of geraniol, and also to simulated the separation process
citronella oil have shown in the table 1. in order to appropriate data of higher purity and yield of
there three main components. Products were analyzed
Apparatus and method by GC. Then, we have an optimum condition from the
The unit operation was used a batch vacuum experiment. We used the optimum condition and
fractionation with capacity 2 L (VTU High Temperature component’s physical properties which was produced
Fractionator Model Pilodist 104 which is shown in figure from the process for simulation, and then we was
1. A simulator ChemCAD 5.0.2 version which is released simulation using ChemCAD simulator to give a
by ChemStation, Inc. Gas chromatography Shimadzu 14 predictive Vapor-Liquid Equilibrium (VLE) for citronellal-
A, column innowax, length 30 m capillary, column rhodinol binary system.
temperature 50 oC – 230 oC with heating rate 2 oC/min
and hold time at 230 oC in 30 min., injector temperature RESULT AND DISCUSSION
280 oC, FID detector temperature 280 oC, and helium as
a gas carrier with rate 4 ml/min. The calculated values were obtained from the
First step, we was determined the physical equilibrium equations:
properties of citronella oil raw material using
conventional method and GC. Separation of citronella oil ( ⎣ )
y i Φ i P = xi γ i PiS ΦSi exp ⎡⎢ν iL P − PiS / RT ⎤⎥
⎦
(1)
Where P = 80 mbar, xi and yi are the mass fractions of
Table 1. Physical properties of citronella oil as raw component i in the liquid and vapor phase,
material. respectively, γi is its activity coefficient, ν iL , its liquid
No. Parameter Results
1 Density 20oC (gr/cm3) 0.8826 molar volume, Φ i and ΦSi , its fugacity coefficients
2 Viscosity (cP) 9.01 under unsaturated and saturated conditions,
Refractive index (20oC)
S
3 1.4664 respectively for pure i and Pi , its vapor pressure at
4 Ester value 31,01 saturation [7,8,9].
5 Acid value 1,13 The simulation process separation of citronella oil
6 Optical rotation -1.275 was conducted in two steps. These were according to
7 Appearance Clearly dark yellow the numerical solution which was giving convergences
8 Solubility in alcohol 95% 1:1 clear and so on of the dynamic simulation. Figure 2 and 3 has shown
the dynamic simulation for this process. Figure 2 was
9 Fatty oil Negative
shown that mass fraction of three components;
10 Kruing oil Negative citronellal, citronellol, and geraniol are respectively
constants in step 1 during the process until 4.5 hours
1.
2.
Agitation Motor
Magnetic stirrer
process time. This was indicating that equilibrium
3. Heating mantle condition could be reached out since the temperature
4. Feed flask
5. Thermocouple in feed flask of process is constant; this condition would be giving a
6. Distillation column
7. Heating mantle constant mass fraction in the distillate during
8.
9.
Cooler
Manometer U tube indicator
equilibrium condition. Step two of simulation process
10. Thermocouple was shown that the separation has a dynamic section
11. Reflux’s unit
12. Manometer U tube and separation of citronellal, citronellol, and geraniol
13. Condensor
14. Vacuum sensor has occurred, figure 3. Citronellal component was
15.
16.
Vacuum pipe
Distillate cooler 21. Control pan separated to give a high purity and has not
17.
18.
Bottle product’s
Fraction flask
22. Trap tube
23. Controlled
contaminated with other components. However,
19. Fraction separator 24. Vacuum pu separation process of citronellol and geraniol has
occurred less than citronellal separation. Citronellol and
geraniol were giving a nearly concentration at the end
Figure 1. Pilot plant batch vacuum fractionation unit flow of process. This was caused that boiling point of both
diagram in the Research Center for Chemistry – components is nearly.
Indonesian Institute of Sciences.

Joddy Arya Laksmono, et al.

 Proceeding of ICCS 2007, Yogyakarta-Indonesia, 24-25 May 2007
Figure 2. First step simulation processes in the batch
vacuum fractionation unit.
Figure 3. Step 2 simulation processes that indicating the
dynamic process.
The separation of citronella-citronellol system has
been in the miscible system. At the molecular level
appreciable negative deviations from Raoult’s law reflect
stronger intermolecular forces between unlike than
between like pairs of molecules. Conversely, appreciable
positive deviations result for solutions in which
intermolecular forces between like molecules are
stronger than between unlike. In this latter case the
forces between like molecules may be so strong in
comparison with those between unlike molecules as to
prevent complete miscibility. In this event the mixture
would form two separated liquid phases over some
composition range.
All data processing was performed using
ChemCAD simulator 5.0.2 version. Figure 4. shown a
Vapor-Liquid Equilibrium (T-xy) curve for binary
citronellal-citronellol system equilibrium. The equilibrium
of vapor-liquid for this system was occurred in the range
of temperature 121 oC – 149 oC under the vacuum
condition. The curve gives information for scaling up
data.
Vapor-Liquid Equilibrium for a binary system, the
phase rule specifies that there are but two degrees of
freedom. Data for such system are invariably taken at
either constant pressure or at constant temperature.
Joddy Arya Laksmono, et al.
3
Figure 4. T-XY diagram for citronellal-citronellol binary
system at a constant vacuum pressure 80 mbar.
Table 2. xy data for citronellal-citronellol with K value
model: SRK.
Mass Fractions
T Deg C P mbar X1 Y1
148.53481 80.00000 0.00000 0.00000
146.65231 80.00000 0.04939 0.11889
144.85136 80.00000 0.09884 0.22398
143.12856 80.00000 0.14835 0.31707
141.48044 80.00000 0.19793 0.39970
139.90329 80.00000 0.24757 0.47320
138.39354 80.00000 0.29727 0.53875
136.94756 80.00000 0.34705 0.59735
135.56178 80.00000 0.39688 0.64986
134.23282 80.00000 0.44678 0.69704
132.95738 80.00000 0.49675 0.73953
131.73257 80.00000 0.54678 0.77790
130.55487 80.00000 0.59687 0.81262
129.42181 80.00000 0.64703 0.84412
128.33075 80.00000 0.69726 0.87277
127.27905 80.00000 0.74755 0.89888
126.26440 80.00000 0.79791 0.92273
125.28468 80.00000 0.84833 0.94457
124.33779 80.00000 0.89882 0.96461
123.42182 80.00000 0.94938 0.98303
122.53481 80.00000 1.00000 1.00000
Since only one degree of freedom remains, x1
may be regarded as the only independent variable in
either case. The equation for the liquid phase of a
binary system in this experiment at constant vacuum
pressure condition was seems in the below [11,12]:
⎛ ∆H ⎞ dT d ln γ 1 d ln γ 2
−⎜ 2 ⎟ dx
= x1 + x2 (2)
⎝ RT ⎠ 1 dx1 dx1
The temperature profile along the column height
was observed and simulated, figure 6. The temperature
range in each stage was observed relatively constant.
These were needed to reach a steady-state operation
of the column. This is important due to the possibly flat
temperature changes in spite of large composition
4 Proceeding of ICCS 2007, Yogyakarta-Indonesia, 24-25 May 2007

Figure 5. xy weigth fraction citronellal-citronellol system. Figure 7. Residu curve map citronellal, citronellol, and
geraniol component by SRK at constant vacuum
pressure 80 mbar.

Table 3. Batch vacuum fractionation simulation

calculation results.
Operation Step 1:

Stream Name Pot Charge Accumulator Pot Residue Distillate

Temp C 27.1525 73.3527 106.2513 73.3543
Pres mbar 80.0000 8.3332 24.6658 8.3332
Enth MJ -30.199 -23.557 -18.680 -0.51210
Vapor mole fraction 0.00000 0.00000 0.00000 0.00000
Total kmol 1.1102 0.5520 0.4928 0.0120
Total kg 171.5441 85.1462 76.3215 1.8510
Total std L m3 0.1995 0.0992 0.0886 0.0022
Flowrates in kmol
CITRONELLAL 0.8419 0.5520 0.2251 0.0120
CITRONELLOL 0.1490 0.0000 0.1487 0.0000
GERANIOL 0.1192 0.0000 0.1190 0.0000
Figure 6. Stage temperature profile in the batch vacuum
fractionation during citronellal-citronellol system Operation Step 2:
separation. Stream Name Accumulator Pot Residue Distillate
Temp C 80.8966 123.4819 101.1986
variations. Before sampling and simulation the Pres mbar 8.3332 24.6658 8.3332
temperature profile, the column top pressure and the Enth MJ -22.234 -0.083731 -0.26895
pressure drop were measured. After sampling the Vapor mole fraction 0.00000 0.00000 0.00000
Total kmol 0.4920 0.0023 0.0060
volume streams at the top of the column and below the Total kg 76.1443 0.3493 0.9317
packing were measured. Total std L m3 0.0885 0.0004 0.0011
The measured streams were compared with those Flowrates in kmol
obtained from the energy balances around the CITRONELLAL 0.2899 0.0000 0.0000
CITRONELLOL 0.1254 0.0003 0.0031
condenser and the reboiler, so that the heat and mass GERANIOL 0.0767 0.0020 0.0029
loss from the column could be calculated. The
compositions of samples were analyzed with gas CONCLUSION
chromatography.
This simulation was used 36 stages in vacuum The simulation of citronellal-citronellol-geraniol
fractionation column, and we tried to simulated was performed with ChemCAD. The essential content
citronellal-citronellol-geraniol separation behaviors. of this paper is a listing of bundles of experimental to
Binary system of citronellal-citronellol separation has found a physical properties which is useful for
shown without azeotropic curves. However, figure 7. was simulation data, and simulation this separation
shown that citronellol-geraniol binary system has phenomenon obtained with binary in non-ideal system,
indicating an azeotropic in (0.879, 0.121) coordinate at in bubble cap tray column and at vacuum pressure.
148.476 oC. Citronellal, citronellol, and geraniol have Also valuable technical information is provided for
had a bubble point at 80 mbar vacuum pressure, construction of pilot scale fractionation column. The
122.534 oC, 148.534 oC, and 150.804 oC respectively. results should be fitted with an experimental data to

Joddy Arya Laksmono, et al.

 Proceeding of ICCS 2007, Yogyakarta-Indonesia, 24-25 May 2007 5

find an accurate data for vapor-liquid equilibrium system.
ACKNOWLEDGEMENT
This research was funded from Indonesian
government, and we should proudly thanks for this
opportunity. We are pleased to Mr. Tasrif for GC data
processing and to Mr. Yogi Hermawan with his fruitful
discussion.
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Joddy Arya Laksmono, et al.