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Fusel oil process separation

Article · January 2011

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 FUSEL OIL PROCESS SEPARATION

Natalia Montoya1, Fernando Córdoba1, Carlos Trujillo1, Iván Gil1, Gerardo Rodríguez1
1
Universidad Nacional de Colombia, Sede Bogotá.

Abstract.
Biofuels industry, especially fuel ethanol industry, has rapidly grown in the last twenty
years. Consequently, by-product utilization has gained attention to make processes more
efficient and profitable. Fusel oil is a by-product in ethanol production. It is mainly composed
by isoamyl alcohol, which is an important raw material for the manufacturing of different
products with a wide chemical market. In this work, a separation process to obtain high purity
isoamyl alcohol from fusel oil was simulated using Aspen Plus. Results are satisfactory in terms
of purity and recovery.

Introduction.
Fuel ethanol production has become in one of the most studied processes in the last
two decades. In countries where ethanol is produced in large scale, by-product utilization is an
important issue for making the global process more profitable and less polluting. Fusel oil is a
by-product in ethanol production. It is a mixture of higher alcohols, composed by isoamyl
alcohol, as major constituent, and in minor proportion by ethanol, water and heavy
components. Isoamyl alcohol is widely used in the manufacturing of different valuable
products such as esters, solvents, lubricant oils, plasticizers, medicinal among others Güvenç
et al (2007).
According to current regulations in Colombia it is expected an increase in ethanol
production, as a consequence, the amount of fusel oil will increase too. In 2012, it is estimated
that around 1400000 liters per day of fuel ethanol will be produced; as a result, around 2800
liter per day of fusel oil will be obtained. Taking into consideration, the mention before, the
high content of isoamyl alcohol in fusel oil –its composition can vary from 60 to 80% [Patil et
al., 2002; Ikeda et al., 1956; Schicktanz et al., 1939)–, and its possibility to be converted in
chemicals with a wide market, it becomes in an opportunity to develop a fusel oil separation
process in order to obtain high purity isoamyl alcohol.

The aim of this work is to design and simulate a separation strategy to obtain isoamyl
alcohol from fusel oil using Aspen Plus Simulator. As case base, a fuel ethanol production plant
with capacity of 400000 liters per day was used. It was assumed a yield of 2 liters of fusel oil
per each 1000 liters of absolute ethanol (Patil et al., 2002; Özgülsün, 2000; Küҫük et al.,
1998).
Thermodynamic Model
According to the suggestions for selecting physical property methods given by Carlson
(1996) and considering the polar and non-electrolyte nature of fusel oil and the moderate
operating conditions of the process under study, NRTL thermodynamic package was chosen to
calculate the activity coefficients in the liquid phase. Else, ideal behavior for the vapor phase
was assumed.

In addition, some experimental data from VLE for ethanol – isoamyl alcohol, ethanol –
water, and LLE for isoamyl alcohol – water systems were obtained using a Fischer Labodest
VLE 602 apparatus and a LLE glass cell, respectively. These data were well fitted to NRTL
thermodynamic model.

Process Description and Simulation

The simulated process involves two main stages and is shown in Figure 1. The first one
consists on separating alcohols and water from heavy components through distillation and the
second one involves purifying of isoamyl alcohol.

Regarding to the first stage, Fusel oil (stream F1) is fed into a distillation column (C-1)
to separate the heavy components (TB>124°C) at the bottom (stream B1) and recover a
mixture of the lighter components at the top (stream D1), which is composed by water,
ethanol and isoamyl alcohol. In the second stage, this mixture (stream F2) is taken into a
stripper (C-2) in order to draw off ethanol and water at the top (stream D2) and to obtain high
purity isoamyl alcohol at the bottom (stream B2). Some isoamyl alcohol is dragged in D2.
Therefore, after cooling, this stream splits into two liquid phases in a decanter (D-1) and the
organic phase (O1) is mixed with the feed stream (F2) to the stripper (C-2).

Preliminary specifications of the distillation columns were estimated using DSTWU short-
cut method. Then, with the information obtained from this procedure, simulations were carried
out using a rigorous method. The distillation column and the stripper were simulated using
Aspen Plus RadFrac model and the liquid-liquid separator was simulated using Aspen Plus
Decanter model. Sensitivity analyses were done by varying parameters such as number of
stages, feed stage and reflux ratio, in order to settle the operating conditions. Also, design
specifications were used to set up purity and recovery of the product in the process.

RadFrac Aspen Plus operation model was used to perform pressure drop calculations for
packed columns. Columns diameters were estimated using PackSizing utility, considering
Sulzer Nutter Ring No-0.7 as a packing. The distillation column and the stripper were also
designed using a non-equilibrium approach in order to establish the effect of mass and heat
transfer correlations in column performance.

Results
 The final results are satisfactory in terms of purity and recovery. They are summarized
in figure 1. High purity and recovery of isoamyl alcohol, 99.7% and 99.3% respectively, are
reached.

Sizing results show that a distillation column of 13.8 ft height and 4 in diameter and a
stripper of 8.2 ft height and 3.5 in diameter, both, packed with Sulzer Nutter Ring 0.7 are able
to manage a volumetric flow of 800 liters per day of fusel oil to obtain 792 liters per day of
high purity isoamyl alcohol.

Stage I: Distillation Stage II: Stripping

HE-3
O1 -5.357 kW
HE-1 10.834 kg/h
-7.743 kW D1 0.531 i-Amyl Alcohol
27.108 kg/h 0.300 Ethanol D2
F1 0.169 Water D-1
0.879 i-Amyl Alcohol 14.177 kg/h
27.641 kg/h 0.024 Ethanol 25 PPM Heavy A1
0.416 i-Amyl Alcohol
0.863 i-Amyl Alcohol 0.095 Water 3.353 kg/h
0.275 Ethanol
0.024 Ethanol 0.002 Heavy 0.042 i-Amyl Alcohol
2 0.309 Water
0.093 Water 2 0.193 Ethanol
29 PPM Heavy
0.020 Heavy 0.765 Water
3 F2 42 PPM Heavy
37.942 kg/h 185
0.780 i-Amyl Alcohol C-2
C-1 0.35 RR
0.103 Ethanol B2
0.116 Water 23.765 kg/h
0.001 Heavy 0.997 i-Amyl Alcohol
B1 5
0.533 kg/h 789 PPM Ethanol
9 0.045 i-Amyl Alcohol 423 PPM Water
2 PPB Ethanol 0.002 Heavy
16 PPB Water
0.955 Heavy HE-4
5.824 kW

HE-2
7.874 kW

Figure 1. Mass and energy balances of the separation strategy

In the case of non-equilibrium approach –Rate-based calculation type- liquid phase

composition and temperature, as well as, mass and heat transfer rates profiles were obtained.
They are shown in figures 2 and 3.
 0,15
1
0,9
0,1

Liquid mass transfer rate kmol/

0,8
Liquid Composition

Water
0,7 0,05
Isoamyl
[mass frac]

0,6
Heavy
0,5 0
Ethanol 2 3 4 5 6 7 8 9
0,4

h
-0,05
0,3 Stage
0,2
-0,1 Water
0,1
Isoamyl
0 -0,15 Heavy
1 2 3 4 5 6 7 8 9 10
Ethanol
Stage -0,2

Figure 2. Liquid composition and mass transfer rate profiles for distillation column C-1
There is a relation between the results from liquid composition and mass transfer rate
profiles. Component mass transfer rates are positive for transfer from vapor to liquid phase. As
can be seen in figure 2, at the top of the distillation column (stages 2 to 5) liquid phase profile
is enriched in isoamyl alcohol, while at the bottom (stages 5 to 9) it is enriched in heavy
components. These facts are caused by components transfer from vapor to liquid phase and
involve a positive change in mass transfer rate profiles. For ethanol and water, mass transfer
rate is low and almost constant; because of this their liquid composition profiles are flat.

200 2
180
Heat transfer rate[ MBtu/h]

0
160 2 3 4 5 6 7 8 9
Temperature [°C]

140 -2
120 Stage
-4
100
80 -6
60 Liquid temperature
-8
40
Vapor temperature
20 -10
0
1 2 3 4 5 6 7 8 9 10 -12

Stage

Figure 3. Temperature and heat transfer profiles for distillation column

As can be seen in figure 3, there was not significant temperature difference between
the two phases. Nevertheless, temperature of vapor phase was higher than temperature of
liquid phase through the entire distillation column. This means that energy was transferred
from liquid to vapor phase, which is evident in the negative values of the heat transfer rate
profile (usual convention is heat transfer rate positive for transfer from vapor to liquid phase).

To develop equilibrium calculations a Murphree efficiency of 0.7 was assumed,

according to average typical values reported on literature for distillation processes (Kister,
1992). From non-equilibrium approach HETP was calculated and is shown in figure 4. An
increase in the HETP to the bottom of the column is observed and the most efficient zone is
located between 6 and 10 segments.

0,8
0,7
0,6
HETP [m]

0,5
0,4
0,3
0,2
0,1
0
1 2 3 4 5 6 7 8 9 10

Segment

Figure 4. Height equivalent of a theoretical plate

In general terms, results from compositions and mass flows are nearly the same using
both, equilibrium and non-equilibrium approaches. It can be explained, taking into account
that the simulated process does not involve chemical reactions or formation of a second liquid
phase inside the columns, which are the factors that most affected non-equilibrium
calculations.

REFERENCES.
1. Carlson, E.C., (1996). “Don’t Gamble with Physical Properties for Simulations”. Chem.
Eng. Prog. 92 (10), 35-46.
2. Güvenç, A., Kapucu, N., Kapucu, H., Aydogan, Ö., Mehmetoglu, Ü., (2007). “Enzymatic
esterification of isoamyl alcohol obtained from fusel oil: Optimization by response
surface methodology”. Enzyme Microb. Technol. 40 (4), 778-785.

3. Ikeda, R.M., Webb, A.D., Kepner, R.E., (1956). “Comparative analysis of fusel oils from
Thompson Seedless, Emperor, and Muscat of Alexandria Wines”. J. Agric. Food Chem. 4
(4), 355–363.

4. Kister, H., (1992). “Distillation Design”. McGraw-Hill, pp 379.

5. Küҫük, Z., Ceylan, K., (1998). “Potential utilization of fusel oil: A kinetic approach for
production of fusel oil esters through Chemical Reaction”. Turk J. Chem. 22, 289-300.
 6. Özgülsün, A., Karaosmanôglu, F., Tüter, M., (2000). “Esterification reaction of oleic acid
with a fusel oil fraction for production of lubricating oil”. JAOCS. 77 (1), 105-109.

7. Patil, A.G., Koolwal S.M., Butala H.D., (2002). “Fusel Oil: Composition, removal and
potential utilization”. Int Sugar J. 104, 51- 58.

8. Schicktanz, S.T., Etienne, A.D., Steele, W.I., (1939). “Analysis of Fusel Oil by Azeotropic
Distillation”. Ind. Eng. Chem. Anal. Ed. 11 (8), 420-422.

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