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
Citronella oil is one of the most interesting essential
oil, mainly it will be used in any industry of flavor and
fragrances, 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 bloodfeeding mosquitoes, ticks, and fleas. As a non-toxic
substance, many people prefer citronella to other
chemical repellants such as DEET (N, N-diethyl-metatoluamide). 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].
* Corresponding author. Tel: +62-21-7560929, Fax : +62-217560549; Email address : joddy_arya_laksmono@yahoo.com

Fractionation distillation is separation of liquid

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 vaporliquid 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.

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

EXPERIMENTAL SECTION
Materials
Citronella oil which is original Java essential oil was
supplied from local commercial home industry with
concentrations of citronellal 32.15%, citronellol 12.95%,
and geraniol 20.54%. The physical properties of
citronella oil have shown in the table 1.
Apparatus and method
The unit operation was used a batch vacuum
fractionation with capacity 2 L (VTU High Temperature
Fractionator Model Pilodist 104 which is shown in figure
1. A simulator ChemCAD 5.0.2 version which is released
by ChemStation, Inc. Gas chromatography Shimadzu 14
A, column innowax, length 30 m capillary, column
temperature 50 oC 230 oC with heating rate 2 oC/min
and hold time at 230 oC in 30 min., injector temperature
280 oC, FID detector temperature 280 oC, and helium as
a gas carrier with rate 4 ml/min.
First step, we was determined the physical
properties of citronella oil raw material using
conventional method and GC. Separation of citronella oil
Table 1. Physical properties of citronella oil as raw
material.
No.
Parameter
Results
1
Density 20oC (gr/cm3)
0.8826
2
Viscosity (cP)
9.01
3
Refractive index (20oC)
1.4664
4
Ester value
31,01
5
Acid value
1,13
6
Optical rotation
-1.275
7
Appearance
Clearly dark yellow
8
Solubility in alcohol 95% 1:1 clear and so on
9
Fatty oil
Negative
10 Kruing oil
Negative
1.
2.
3.
4.
5.
6.
7.
8.
9.
10.
11.
12.
13.
14.
15.
16.
17.
18.
19.

Agitation Motor
Magnetic stirrer
Heating mantle
Feed flask
Thermocouple in feed flask
Distillation column
Heating mantle
Cooler
Manometer U tube indicator
Thermocouple
Refluxs unit
Manometer U tube
Condensor
Vacuum sensor
Vacuum pipe
Distillate cooler
21. Control pan
Bottle products
22. Trap tube
Fraction flask
23. Controlled
Fraction separator
24. Vacuum pu

Figure 1. Pilot plant batch vacuum fractionation unit flow

diagram in the Research Center for Chemistry
Indonesian Institute of Sciences.

Joddy Arya Laksmono, et al.

to produced three main component was used a batch

vacuum fractionator in the vacuum pressure condition
40 80 mbar and temperature was 120 oC 150 oC.
We assumed that the separation has a binary system
citronellal-rhodinol. This process was determined the
physical properties of citronellal, citronellol, and
geraniol, and also to simulated the separation process
in order to appropriate data of higher purity and yield of
there three main components. Products were analyzed
by GC. Then, we have an optimum condition from the
experiment. We used the optimum condition and
components physical properties which was produced
from the process for simulation, and then we was
simulation using ChemCAD simulator to give a
predictive Vapor-Liquid Equilibrium (VLE) for citronellalrhodinol binary system.
RESULT AND DISCUSSION
The calculated values were obtained from the
equilibrium equations:
(1)
y i i P = xi i PiS Si exp iL P PiS / RT

Where P = 80 mbar, xi and yi are the mass fractions of

component i in the liquid and vapor phase,
respectively, i is its activity coefficient, iL , its liquid

molar volume, i and Si , its fugacity coefficients

under
unsaturated
and
saturated
conditions,
S
respectively for pure i and Pi , its vapor pressure at
saturation [7,8,9].
The simulation process separation of citronella oil
was conducted in two steps. These were according to
the numerical solution which was giving convergences
of the dynamic simulation. Figure 2 and 3 has shown
the dynamic simulation for this process. Figure 2 was
shown that mass fraction of three components;
citronellal, citronellol, and geraniol are respectively
constants in step 1 during the process until 4.5 hours
process time. This was indicating that equilibrium
condition could be reached out since the temperature
of process is constant; this condition would be giving a
constant mass fraction in the distillate during
equilibrium condition. Step two of simulation process
was shown that the separation has a dynamic section
and separation of citronellal, citronellol, and geraniol
has occurred, figure 3. Citronellal component was
separated to give a high purity and has not
contaminated with other components. However,
separation process of citronellol and geraniol has
occurred less than citronellal separation. Citronellol and
geraniol were giving a nearly concentration at the end
of process. This was caused that boiling point of both
components is nearly.

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 Raoults 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.

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]:
d ln 1
d ln 2
H dT
(2)

= x1
+ x2
2 dx
dx1
dx1
RT 1
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

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
calculation results.

fractionation

simulation

Operation Step 1:
Stream Name
Pot Charge Accumulator
Temp C
27.1525
73.3527
Pres mbar
80.0000
8.3332
Enth MJ
-30.199
-23.557
Vapor mole fraction 0.00000
0.00000
Total kmol
1.1102
0.5520
Total kg
171.5441
85.1462
Total std L m3
0.1995
0.0992
Flowrates in kmol
CITRONELLAL
0.8419
0.5520
CITRONELLOL
0.1490
0.0000
GERANIOL
0.1192
0.0000

Figure 6. Stage temperature profile in the batch vacuum

fractionation
during
citronellal-citronellol
system
separation.

variations. Before sampling and simulation the

temperature profile, the column top pressure and the
pressure drop were measured. After sampling the
volume streams at the top of the column and below the
packing were measured.
The measured streams were compared with those
obtained from the energy balances around the
condenser and the reboiler, so that the heat and mass
loss from the column could be calculated. The
compositions of samples were analyzed with gas
chromatography.
This simulation was used 36 stages in vacuum
fractionation column, and we tried to simulated
citronellal-citronellol-geraniol
separation
behaviors.
Binary system of citronellal-citronellol separation has
shown without azeotropic curves. However, figure 7. was
shown that citronellol-geraniol binary system has
indicating an azeotropic in (0.879, 0.121) coordinate at
148.476 oC. Citronellal, citronellol, and geraniol have
had a bubble point at 80 mbar vacuum pressure,
122.534 oC, 148.534 oC, and 150.804 oC respectively.

Joddy Arya Laksmono, et al.

Pot Residue
106.2513
24.6658
-18.680
0.00000
0.4928
76.3215
0.0886
0.2251
0.1487
0.1190

Distillate
73.3543
8.3332
-0.51210
0.00000
0.0120
1.8510
0.0022
0.0120
0.0000
0.0000

Operation Step 2:
Stream Name
Accumulator
Temp C
80.8966
Pres mbar
8.3332
Enth MJ
-22.234
Vapor mole fraction 0.00000
Total kmol
0.4920
Total kg
76.1443
Total std L m3
0.0885
Flowrates in kmol
CITRONELLAL
0.2899
CITRONELLOL
0.1254
GERANIOL
0.0767

Pot Residue
123.4819
24.6658
-0.083731
0.00000
0.0023
0.3493
0.0004

Distillate
101.1986
8.3332
-0.26895
0.00000
0.0060
0.9317
0.0011

0.0000
0.0003
0.0020

0.0000
0.0031
0.0029

CONCLUSION

The simulation of citronellal-citronellol-geraniol

was performed with ChemCAD. The essential content
of this paper is a listing of bundles of experimental to
found a physical properties which is useful for
simulation data, and simulation this separation
phenomenon obtained with binary in non-ideal system,
in bubble cap tray column and at vacuum pressure.
Also valuable technical information is provided for
construction of pilot scale fractionation column. The
results should be fitted with an experimental data to

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

find an accurate data for vapor-liquid equilibrium system.

6.

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.

7.

REFERENCES

1.

2.
3.

4.

5.

Egi Agustian, Asep Kadarohman, Anny Sulaswatty,

Fractionation of Citronellal from Citronella oil Using
Vacuum Distillation Technique, Prosiding Seminar
Fundamental dan Aplikasi Teknik Kimia 2004,
Surabaya, 7 8 Desember.
Sitorus, M., Esterifikasi Rodinol dari Minyak Sereh
dengan Anhidrida Asam Karboksilat, Thesis S2
Universitas Gajah Mada, Yogyakarta, 1995.
Haznan Abimanyu, Anny Sulaswatty, Wuryaningsih
dan Egi Agustian.,
Teknologi Distilasi Terfraksi
Dalam Pemurnian Komponen Minyak Atsiri,
Prosiding
Pemaparan
Hasil
Litbang
Ilmu
Pengetahuan Teknik 2003, Bandung.
Sami
Pelkonen,
Andrzej
Grak,
Andr
Ohligschlger, Ruth Kaesemann, Experimental
Study on Multicomponent Distillation in Packed
Columns, Chemical Engineering and Processing,
40, (2001), 235-243.
P. Pllmann, M.H. Bauer, and E. Bla,
Investigation of Vapor-Liquid Equilibrium of Nonideal Multicomponent Systems, Gas. Sep. Purif.,
Vol. 10, No. 4, pp. 225-241, 1996.

Joddy Arya Laksmono, et al.

8.

9.

10.

11.
12.

Alberto Arce, JoseMartnez-Ageitos, Eva Rodil,

Ana Soto, Phase Equilibria Involved in Extractive
Distillation
of
2-methoxy-2methylpropaneqmethanol Using 1-butanol as
Entrainer, Fluid Phase Equilibria, 171, 2000, 207
218.
F. B. Petlyuk, Simple Methods for Predicting
Feasible Sharp Separations of Azeotropic
Mixtures, Theoretical Foundations of Chemical
Engineering, Vol. 32, No. 3, 1998, pp. 245253.
Translated
from
Teoreticheskie
Osnovy
Khimicheskoi Tekhnologii, Vol. 32, No. 2, 1998,
pp. 279287. Original Russian Text Copyright
1998 by Petlyuk.
Arjun Vadapalli, J.D. Seader, A Generalized
Framework for Computing Bifurcation Diagrams
Using Process Simulation Programs, Computers
and Chemical Engineering, 25, (2001), 445464.
F. G. Smith III, R. A. Dimenna, Simulation of a
Batch Chemical Process Using Parallel
Computing with PVM and Speedup, Computers
and Chemical Engineering, 28, (2004), 1649
1659.
R. Schneider, F. Sander, A. Gorak, Dynamic
Simulation of Industrial Reactive Absorption
Processes,
Chemical
Engineering
and
Processing, 42, (2003), 955-964.
Perry, R.H & D. Green, 1984. Perrys Chemical
Engineering Handbook. Mc Graw-Hill Company,
New York.
J.M. Smith, H.C. Van Ness, Introduction to
Chemical Engineering Thermodynamics, 3rd Ed.
McGraw-Hill International book company, 290364,
1975,
Singapore.