Вы находитесь на странице: 1из 16



Study of the Fusel Oil Distillation Process

Marcela C. Ferreira, Antonio J. A. Meirelles, and Eduardo A. C. Batista*
ExTrAE, Laboratory of Extraction, Applied Thermodynamics and Equilibrium, Department of Food Engineering, Faculty of Food
Engineering, University of Campinas-UNICAMP, 13083-862, Campinas, SP, Brazil

ABSTRACT: Fusel oil is a byproduct obtained from bioethanol distilleries, composed of a mixture of higher alcohols such as
isoamyl alcohol, isobutyl alcohol, and others. This study aimed to evaluate the industrial distillation process of fusel oil to obtain
isoamyl alcohol using the Aspen Plus simulator, considering fusel oil as a mixture of nine components. Fusel oil samples collected
in Brazilian industrial mills were analyzed by gas chromatography. An investigation of phase equilibrium (vapor−liquid
equilibrium and liquid−liquid equilibrium) was carried out for the components involved in this mixture. Three configurations for
the fusel oil separation process were proposed. The best design with minimum total annual cost (TAC) resulted in a recovery of
99.53% of isoamyl alcohol of product containing the isomers isoamyl alcohol (0.818 w/w) and active amyl alcohol (0.178 w/w).
Dynamic control of this configuration was investigated, and the results show that reasonable control performance can be

1. INTRODUCTION present in the fusel oil sidestream in order to maximize its

The production of bioethanol generates byproducts, such as fusel economic value. The higher alcohol stream removed from the
oil, which consists of a mixture of higher alcohols. In countries bioethanol rectifying column is collected and goes to a decanter,
where large quantities of ethanol are produced, like Brazil, alter- where the fusel oil is washed in countercurrent with water. In this
natives for the use of these byproducts are of great importance to process two phases are formed. At the top of the decanter fusel oil
make ethanol production less polluting and more profitable. is collected, and at the bottom there is a mixture rich in water and
In Brazil, fusel oil is generally produced in the proportion of ethanol, which is returned to the columns of the bioethanol
2.5 L per 1000 L of ethanol. Brazilian ethanol production process.
(anhydrous and hydrated) in 2011 exceeded 27 billion liters. At As mentioned before, fusel oil is a mixture of several alcohols,
this scale a total of 67.5 million liters of fusel oil can be generated which limits its direct use as a solvent. The higher alcohols
per year. present in fusel oil are considered natural products, which gives
According to Patil et al.,1 the term fusel oil is used to designate them high commercial values.3 Isoamyl alcohol, the main com-
a mixture of higher alcohols obtained during distillation of ponent of fusel oil, can be used in the production of organic
bioethanol. Higher alcohols are those consisting of more than esters, which are used as industrial solvents, flavoring agents, and
two carbon atoms such as isoamyl alcohol, isobutanol, propanol, plasticizers.
butanol, and others. Due to the presence of water in fusel oil, heterogeneous
Values of the relative volatilities of higher alcohols as a function azeotropes form between water and most of the higher alcohols.
of ethanol concentration in the liquid phase were investigated by The separation of a heterogeneous azeotrope mixture is much
Batista and Meirelles2 via simulation of a liquid−vapor flash. The easier than that of a homogeneous azeotrope mixture, because
higher alcohols exhibit a decrease in volatility as the ethanol the liquid−liquid equilibrium that occurs in the decanter can be
concentration in the liquid phase increases, acting as light used to facilitate this separation.4 Isoamyl alcohol and water form
components in the diluted ethanol range and as heavy com- a heterogeneous azeotrope at atmospheric pressure and 95.1 °C,
ponents in the concentrated ethanol range. Because of this with a composition of 50.4% w/w of isoamyl alcohol.
behavior they should be classified as components with Fusel oil cannot be discarded directly into the environment,
intermediate volatility.
since it would cause undesirable environmental impacts. Some
In a bioethanol rectifying column, the region near its bottom
authors have indicated direct applications of fusel oil: it can be
presents low ethanol contents; therefore, the volatility of higher
burned to supply energy in the distilleries5 or it can be added to
alcohols is increased and they concentrate in the vapor phase,
rising up the column. In regions near the top of this column, the diesel fuel to improve the cetane index.1 Considering the amount
ethanol content increases; the volatility of higher alcohols of fusel oil in Brazil, a plant capable of producing isoamyl alcohol
therefore decreases and they tend to concentrate in the liquid from fusel oil obtained from different distilleries is an interesting
phase, going back down the column. Thus, the higher alcohols industrial application, since this alcohol is highly valued; its
form a cycle inside the column, reaching their maximum market price is approximately 3 times the price of ethanol fuel.
concentration in regions near the bottom of the rectifying
column, from where they must be withdrawn so not to interfere Received: March 12, 2012
in operation of the column. Revised: December 18, 2012
Distilleries in Brazil do not use fusel oil but instead sell it to Accepted: January 10, 2013
other industries. The distilleries efficiently remove ethanol Published: January 10, 2013

© 2013 American Chemical Society 2336 dx.doi.org/10.1021/ie300665z | Ind. Eng. Chem. Res. 2013, 52, 2336−2351
Industrial & Engineering Chemistry Research Article

There are many studies in literature that report the application Table 1. Composition of Fusel Oil
of fusel oil for obtaining esters by enzymatic or biotechnological
mass fraction
processes,5−8 but most studies use the pure isoamyl alcohol in
their experiments without considering the fusel oil purification average (samples normalized
components sample 1 sample 2 1 and 2) composition
process. Simulation studies (both static and dynamic) for fusel oil
isoamyl alcohol 0.5305 0.5438 0.5372 0.5570
purification processes were not studied.
active amyl 0.1477 0.0850 0.1164 0.1207
The present work investigated fusel oil purification using alcohol
computational simulation. For this study, nine compounds were isobutanol 0.0561 0.0733 0.0647 0.0671
selected to represent the fusel oil: water, ethanol, 3-methyl-1- butanol 0.0074 0.0036 0.0055 0.0057
butanol (isoamyl alcohol), 2-methyl-1-butanol (active amyl pentanol 0.0002 0.0005 0.0003 0.0003
alcohol), isobutanol, pentanol, butanol, propanol, and methanol. propanol 0.0032 0.0149 0.0090 0.0094
ethanol 0.0681 0.0989 0.0835 0.0866
2. CHROMATOGRAPHIC ANALYSIS methanol 0.0004 0.0000 0.0002 0.0002
water 0.1478 0.1475 0.1476 0.1531
Fusel oil samples from two bioethanol production plants in the total 0.9613 0.9674 0.9644 1.0000
state of São Paulo, Brazil, were analyzed for detailed character-
ization of their compositions. The samples were coded as
For analysis of the alcohols, a gas chromatograph (Shimadzu OF PHASE EQUILIBRIUM
GC 17 A) with automatic injector (Shimadzu AOC 20i), flame For accurate design and optimization of the fusel oil distillation
ionization detector (FID), and an Agillent DB-624 column (6% processes, reliable knowledge of the phase equilibrium behavior
phenylcyanopropyl and 94% dimethylpolysiloxane, measuring is required. In this work, the description of phase equilibrium
60 m in length, 0.25 mm in internal diameter, and 1.4 μm in film [vapor−liquid equilibrium (VLE) or liquid−liquid equilibrium
thickness) was used. (LLE)] of the components found in fusel oil was investigated
Analyses were conducted using methanol as the solvent. using the parameters found in the Aspen Plus databank
Operational conditions of the chromatograph were as follows. (commercial simulator from Aspen Technology). The phase
The injection and detection temperatures were fixed at 230 °C, equilibrium was calculated using the parameters for each binary
subsystem of the simulator and compared to the experimental
and column pressure was 178 kPa. The temperature program
data found in the literature.
used for the column was held at 40 °C for 4 min, 1 °C/min ramp 3.1. Vapor−Liquid Equilibrium (VLE). Vapor−liquid
to 60 °C, hold at 60 °C for 1 min, ramp from 60 to 83 °C at a rate equilibrium data for 36 binary parameters were investigated
of 5 °C/min, from 83 to 88 °C at a rate of 0.5 °C/min, and from using experimental data collected from several published
88 to 210 °C at a rate of 15 °C/min. The sample injection volume studies.10−27 There are no experimental measurements of
was 1.0 μL with split ratio of 1:30. Hydrogen was used as ignition vapor−liquid equilibrium using fusel oil, and even equilibrium
gas and helium as carrier gas, with a flow of 1.50029 mL/min and data for the binary systems considered in this work are quite
linear velocity of 26.2437 cm/s. The total run time was 50 min. scarce. The aim of this part was just to check the parameters,
For analysis of methanol, water was used as the solvent, since the efficiency of the simulations is related to the quality of
utilizing the following temperature program: hold at 40 °C for these parameters in describing VLE. The NRTL model was
4 min, 1 °C/min ramp to 60 °C, hold at 60 °C for 1 min, then a chosen for calculating the activity coefficient, and the fugacity
ramp 7 °C/min to 210 °C, and hold at 210 °C for 1 min. The coefficient of the vapor phase was calculated by the Virial
injection volume was 1.5 μL and the other conditions were equation in association with the Hayden−O’Connell equation.
identical to the previous procedure. The NRTL and Hayden−O’Connell models were used by Bessa
The components were quantified by the external standard et al.28 to reproduce experimental process data from Brazilian
technique based on the construction of calibration curves for the bioethanol distilleries, leading to lower deviations. Due to the
eight components, except water. All standard components were similarity of the systems, these models were chosen in this work.
chromatographic grade and purchased from Sigma Aldrich. The equilibrium was calculated using the NRTL interaction
Quantification of water was performed in triplicate using a Karl parameters available in the Aspen Plus databank and compared
Fischer titrator (model Metrohm 710 KF Tritino). to the experimental data. Also it was calculated the average
Table 1 summarizes the results of fusel oil samples from two absolute deviation of the vapor phase molar fraction. The
bioethanol plants, analyzed by GC and Karl Fischer. It can be criterion defined for accepting the parameters present in
the database of the simulator was that the average deviations of
observed that isoamyl alcohol, active amyl alcohol, water,
the experimental and calculated mole fraction must be less than
isobutanol, and ethanol are the major compounds. 0.03. On the other hand, if the deviation was higher than this
The presence of heavier compounds, which were not criterion, the NRTL parameters for this binary were readjusted.
quantified, was observed in all chromatograms. These For the binaries that had no parameters in Aspen Plus, thermo-
components are possibly esters and alcohols with more than dynamic modeling of the experimental data was performed with
six carbons.9 However, because they were found in minimal the commercial simulator.
concentrations, they were not taken into account in this study. Isoamyl alcohol + water13 and pentanol + water14 presented
In order to obtain a single fusel oil composition to be used in absolute deviations in vapor phase composition greater than
the simulations, compositions of samples 1 and 2 were averaged, 0.03. Consequently, regression of the Aspen Plus parameters
since they are very similar. A normalization of this composition from experimental data was carried out for these two binaries.
was carried out, resulting in the normalized fusel oil composition Before the readjustment, the average deviations in the vapor
also shown in Table 1. phase were 0.037 for isoamyl alcohol + water and 0.039 for
2337 dx.doi.org/10.1021/ie300665z | Ind. Eng. Chem. Res. 2013, 52, 2336−2351
Industrial & Engineering Chemistry Research Article

Figure 1. T−x−y diagram for the water (1) + isoamyl alcohol (2) system, at 1 atm (experimental data from Cho et al.13 and calculated results are shown).

pentanol + water, and after readjustment they were reduced to columns were simulated at atmospheric pressure and using a
0.007 and 0.016, respectively. This new parameter databank Murphree efficiency equal to 0.7.
enables more accurate computational simulations of fusel oil in In the simulations conducted the following responses were
distillation columns. evaluated: mass fraction of isoamyl alcohol in final product (IA),
Figure 1 shows the T−x−y diagram for the isoamyl alcohol + the percentage of isoamyl alcohol recovery (RE), and specific
water13 system at 1 atm and the VLE results obtained by the steam consumption (SSC). The variable IA is obtained directly
NRTL parameters, before and after the readjustment, where the in the simulations, while the variable recovery (RE) was obtained
presence of a heterogeneous azeotrope can be verified. by eq 1.
3.2. Liquid−Liquid Equilibrium (LLE). From the nine ⎛ isoamyl alcohol mass flow in the bottom stream ⎞
components considered for fusel oil in this study, it was found RE (%) = 100⎜ ⎟
that five binaries present restricted miscibility at room temper- ⎝ isoamyl alcohol mass flow in the feed stream ⎠
ature: water + 3-methyl-1-butanol, water + 2-methyl-1-butanol, (1)
water + isobutanol, water + butanol, and water + pentanol. The energy requirements of the reboiler are industrially
Therefore, it was necessary to search for ternary LLE data whose expressed through the specific steam consumption, which is the
components were among those studied in the present work, and mass of steam consumed in the heat exchanger per kg of final
12 data sets were found in the literature.29−32 Several tests were product produced. However, the simulator presents the energy
performed to select the thermodynamic model that best consumed in the reboiler in kcal/h. Hence, SSC is calculated
represents the experimental data, also evaluating the libraries of using eq 2, where the heat of vaporization (λ) assumes the value
the parameters present in the simulator. of 503.8 kcal/kg33 (considering saturated steam at a pressure of
For the thermodynamic parameters of the LLE, the phase 5 kgf/cm2).
composition of the system was better described by the
UNIQUAC model (using the LLE-LIT parameters of the ⎛ kg steam ⎞
Aspen databank) when compared to the NRTL model. SSC⎜ ⎟
⎝ kg product ⎠
Because it is possible to use different parameter banks in the
same simulation in Aspen Plus, it was decided to use the energy (kcal/h)
UNIQUAC model to describe the LLE in the decanters of the λ (kcal/kg vapor) × product mass flow (kg product/h)
following simulations. (2)

4. COMPUTATIONAL SIMULATIONS OF FUSEL OIL 4.1. Conceptual Design of the Ternary System: Water +
DISTILLATION PROCESS Ethanol + Isoamyl Alcohol. Distillation of the ternary system
water + ethanol + isoamyl alcohol was studied to better
Simulations were conducted using the commercial simulator understand the process of heterogeneous azeotropic distillation
Aspen Plus from Aspen Technology. In all simulations, the of fusel oil, considering the following fusel oil composition (in
distillation column was represented using the RadFrac model, mass fraction): 0.16 of water, 0.24 of ethanol, and 0.60 of isoamyl
where calculations are performed based on the MESH equations. alcohol. A column with 10 trays was modeled with feed at its
Numbering of the stages in the simulations starts at the top of the middle, plus two stages, where the first stage corresponds to the
column, where the condenser is represented by the first stage and condenser and the last one represents the reboiler, totalizing 12
the reboiler as the last stage. The internal algorithm used by the stages. The reflux ratio was set at 1.5 and the bottom mass flow
simulator to solve the equations was Newton. All distillation was defined as the maximum mass flow which allows for
2338 dx.doi.org/10.1021/ie300665z | Ind. Eng. Chem. Res. 2013, 52, 2336−2351
Industrial & Engineering Chemistry Research Article

Figure 2. Ternary diagram for water + ethanol + isoamyl alcohol at 1 atm and mass balance lines of the one column design.

obtaining a bottom product with isoamyl alcohol purity greater

than 99%.
The vapor−liquid−liquid equilibrium (VLLE) diagram for
this ternary system can be observed in Figure 2. A distillation
boundary divides the system into two distillation regions. The
location of the feed composition and the results for the distillate
and bottom compositions for simulation are also marked in
Figure 2, as well as the liquid composition profile of the column.
From the analysis of this figure, it is observed that it is a possible
distillation process, since the points of composition of distillate
and bottom products are close to a residual curve and these
points are aligned with the point of feed composition. Using a
bottom product mass flow rate of 51.77 kg/h, a purity of 99%
isoamyl alcohol in this stream was acquired. It was noted that
trays 2−10 exhibited separation of liquid phases in the simulated
process. This is in accordance with the diagram shown in Figure
2, since the points of the liquid composition of these trays are
located in the VLLE region.
It was observed that the distillate of this column still has a high
concentration of isoamyl alcohol (0.18 in mass fraction). The
point of the distillate composition is located near the distillation
boundary in the diagram. This boundary cannot be crossed with a Figure 3. Configuration for the ternary system.
single column distillation; consequently, in this case it is not
possible to obtain pure components. But a decanter can be used previous column simulation, but with a bottom mass flow of
to cross the distillation boundary and consequently obtain purer 60 kg/h (total input mass flow of isoamyl alcohol in the process),
products with greater recovery. and the minimum reflux ratio required was determined to
This observation allowed for developing the configuration of generate a bottom product with a purity of at least 0.99 in isoamyl
the ternary system as shown in the flow diagram in Figure 3, alcohol mass fraction. The reflux ratio acquired was 18. The
where a liquid sidestream (sidestream) is removed from the column sidestream was withdrawn from the column at a mass flow of
and feeds the decanter. The organic phase (organic) rich in 43 kg/h at stage 9 (corresponding to tray 8) and the organic
higher alcohols returns to the column, while the aqueous phase phase returned to the column in stage 10. Operating conditions
(aqueous) is removed from the process. The organic stream of the decanter were atmospheric pressure and temperature of
returns to the distillation column at one stage below the stage 86.3 °C, the same temperature of the stage where the sidestream
where the sidestream is removed, in order to maintain the liquid was withdrawn. The results for the compositions of the main
mass flow in the column. streams are shown in Figure 4. With this configuration a mass
Still analyzing the ternary system, a simulation was performed fraction of 0.99 isoamyl alcohol was obtained along with 99%
with the column operating under the same conditions as in the recovery of this alcohol. It was observed that inclusion of the
2339 dx.doi.org/10.1021/ie300665z | Ind. Eng. Chem. Res. 2013, 52, 2336−2351
Industrial & Engineering Chemistry Research Article

Figure 4. Ternary diagram for water + ethanol + isoamyl alcohol at 1 atm and mass balance lines for configuration of Figure 3.

Figure 5. Liquid composition profile A: one column, mass flow bottom of 60 kg/h.

decanter led to a decrease in the number of trays presenting the the column, with water exiting in the bottom stream, making it
formation of two liquid phases, since part of the water was impossible to obtain isoamyl alcohol with high purity. It should
removed from the process via the aqueous stream. be noted that the composition shown in Figure 5 refers to the
4.2. One-Column Process: Multicomponent System. overall composition of the liquid phase. A configuration was
The product of interest in this study is the isoamyl alcohol, and proposed (named configuration A) in which this column
this is one of the heaviest components present in fusel oil. Thus, operates with increased bottom stream mass flow rate. This
in the distillation process this component is obtained at high configuration will be studied later.
purity in the bottom stream. In order to evaluate the impact of Profile B is obtained in situations where the bottom mass flow
the mass flow of the bottom stream in the isoamyl alcohol is less than 60 kg/h. In these cases, it is possible to obtain a stream
purification process, preliminary simulations were carried out of high-purity isoamyl alcohol, and liquid phase separation is not
using a configuration with only one distillation column with the observed in the column. Nevertheless, the low mass flow results
following specifications: feed mass flow of 100 kg/h, column with in low recoveries, and therefore, it is necessary to include other
30 stages, feed at stage 15 (normalized composition shown in unit operations in the process to increase recovery. The
Table 1), and reflux ratio of 5.75. In these simulations, the configuration in which this column operates with a bottom
bottom product mass flow varied from 40 to 70 kg/h. mass flow lower than 60 kg/h was defined as configuration B and
It was possible to note two main composition profiles of the it will be discussed later.
liquid phase in the column, referred to as profile A (Figure 5) and Water is a limiting factor in this distillation process because it
profile B (Figure 6). generates heterogeneous azeotropes with various compounds
Profile A is found when the bottom mass flow is equal to or present in the fusel oil, which then leads to the emerging of two
greater than 60 kg/h. In this case, two liquid phases emerge inside liquid phases. Hence, the reduction of water content in the feed
2340 dx.doi.org/10.1021/ie300665z | Ind. Eng. Chem. Res. 2013, 52, 2336−2351
Industrial & Engineering Chemistry Research Article

Figure 6. Liquid composition profile B: one column, mass flow bottom of 40 kg/h.

stream facilitates fractionation of the solution, this observation This phenomenon is associated with the heterogeneous
aided in the development of a new configuration, called con- azeotropic point between water and isoamyl alcohol.
figuration C, described later. In the ternary system, inclusion of the decanter led to a
It was observed in all cases that it is not possible to obtain only decrease in the number of trays in which there is the formation of
isoamyl alcohol (3-methyl-1-butanol) in the bottom stream due two liquid phases in the column distillation. Thus, the same
to the presence of active amyl alcohol (2-methyl-1-butanol). configuration was used for the multicomponent system. It was
These alcohols are isomers and have relative volatilities close to necessary to include a heat exchanger in the previously proposed
unity, which complicates the separation process. Although the configuration to cool the stream directed to the decanter, since
product of interest in this study is isoamyl alcohol, results were this operates at 25 °C. A schematic for this proposed con-
expressed as a sum of the mass fraction of isoamyl alcohol and figuration, defined as configuration A, is shown in Figure 7. A
active amyl alcohol. This is a reasonable approximation, since distillation column with 30 trays and reflux ratio of 5.75 was used.
commercial isoamyl alcohol consists of a mixture of these In order to analyze the influence of sidestream mass flow on
alcohols, verified by GC analysis. The small difference in the the process, simulations were carried out by varying this variable
boiling point (only 2.5 °C) between the isoamyl alcohol and from 10 to 100 kg/h. Withdrawal of the sidestream was evaluated
the active amyl alcohol difficults their separation. Therefore, a at three stages, 5, 15, and 25, corresponding to trays 4, 14, and 24,
large number of trays is needed for distillation separation of these and the organic stream always returned to the distillation column
substances as well as a high reflux ratio, which makes this process one tray below the withdrawal tray.
impracticable. An alternative to a tray distillation process is the It was found that an increased mass flow of the withdrawn
sidestream resulted in increased mass flow of water in the
use of a packed column, which, due to the greater interfacial area,
aqueous stream of decanter and, consequently, an increase in the
increases considerably the mass transfer, reducing the size of the
purity of isoamyl alcohol in the bottom stream of the distillation
distillation column. Liu et al.34 developed a structured packing
column. However, it can be noted that when exceeding a
for a distillation column in order to separate these two isomers,
determined value of the sidestream mass flow (approximately
obtaining active an amyl alcohol yield of 80% with 99% purity. 50 kg/h), the mass flow of water in the aqueous stream and the
For the proposed configurations, it was established that the purity of isoamyl alcohol in the bottom stream do not exhibit
sum of the compositions of isoamyl alcohol and active amyl significant variation. There is a tendency for water content in the
alcohol in the product stream should be equal to 0.996. This was aqueous phase to remain constant at a value between 8 and
maintained so as to compare the different configurations. 9.3 kg/h and the mass fraction of isoamyl alcohol in the bottom
For the three proposed configurations, a main column with 30 stream was maintained between 0.81 and 0.82.
trays was simulated. In preliminary simulations, this number of Considering the example where the withdrawn sidestream was
trays proved to be reasonable to promote the desired separation. located at stage 5 and comparing the results for sidestream mass
Two additional stages are included in each configuration, flow rates of 60 and 100 kg/h, it was expected that with an
referring to the reboiler and the condenser. increase of 40 kg/h in mass flow of the sidestream it would be
The normalized composition shown in Table 1 was used with a possible to remove more water from the process via the aqueous
mass flow of 100 kg/h and fed in the middle of the column. The stream from the decanter. However, the mass flow of water in this
final product mass flow was fixed at 67.77 kg/h. This value sidestream increased only from 9.23 to 9.28 kg/h, and the purity
corresponds to the sum of the isoamyl alcohol (55.7 kg/h) and of the isoamyl bottom stream increased from 0.8191 to 0.8194.
active amyl alcohol mass flows (12.07 kg/h) in the feed stream, The aqueous and organic streams of the decanter are deter-
ensuring higher recoveries. mined by mass balance using the conditions of LLE at 25 °C. The
4.3. Configuration A. In one-column process simulations restricted solubility of water in higher alcohol rich phase can be
with bottom mass flow equal to or greater than 60 kg/h (profile emphasized in the LLE. Nevertheless, this solubility is sufficient
A), the emergence of two liquid phases in the distillation column to carry some water to the organic stream. As the increase in mass
was noticed, which significantly affects the column performance. flow of sidestream also reflects the increased mass flow of isoamyl
2341 dx.doi.org/10.1021/ie300665z | Ind. Eng. Chem. Res. 2013, 52, 2336−2351
Industrial & Engineering Chemistry Research Article

Figure 7. Flowsheet of the configuration A.

alcohol in this stream, then greater transfer of water to the rate in one side of the DWC is also reduced; therefore in these
organic stream occurs in the decanter, therefore limiting preliminary simulations, it was not possible to remove a sufficient
the amount of water that can be removed from the process via amount of water with the sidestream. The water is a limiting
the aqueous stream from the decanter. factor in this distillation process because it generates
For the withdrawn sidestream at stage 5, sidestream mass flow heterogeneous azeotropes with various compounds present in
rates greater than 60 kg/h are sufficient to eliminate the effect of the fusel oil. Consequently, the isoamyl alcohol was not obtained
formation of two liquid phases in the column, permitting with high purity in the bottom stream of this design. Further
purification of the isoamyl alcohol. On the other hand, when the investigations must be carried out, and the results from this paper
sidestream is removed at stages 15 and 25, the tested flow rates provide the basis for future developments of the use of DWC for
were not sufficient to eliminate formation of two liquid phases in the fusel oil distillation.
the column, leading to a lower purity of isoamyl alcohol in the 4.4. Configuration B. As mentioned previously, it is possible
bottom stream. Due to the best results, it was defined that the to achieve a high purity of isoamyl alcohol using a low flow rate of
sidestream be withdrawn at stage 5 in configuration A, with a the bottom product in a process that consists of only one
mass flow of 60 kg/h. distillation column, as seen in profile B of Figure 6. This system
In configuration A the decanter operated at 25 °C; therefore, it presents low efficiency due to the great loss of higher alcohols in
is necessary to cool the sidestream to that temperature. Water at the distillate of the column.
20 °C was also used as a cooling fluid. The mass flow input of the A flowsheet was proposed including a second distillation
cooling fluid was 120 kg/h, double that of the sidestream flow column in order to recover the remaining isoamyl alcohol lost in
rate. In the simulator, the output temperature of the side- the distillate of the first column. Preliminary tests were carried
stream leaving the heat exchanger (sidestream* in Figure 7) was out and it was found that the top stream of the first distillation
specified at 25 °C. column showed phase separation at 25 °C. Therefore, it was
In this configuration, the reflux ratio was adjusted in order to decided to include a decanter to promote partial removal of water
obtain the desired composition of isoamyl alcohol and active from this stream, facilitating the second distillation column
amyl alcohol in the product, reaching a value of 3.3, with SSC process. A schematic for this proposed configuration, defined as
equal to 1.1321 kg steam/kg product. configuration B, is shown in Figure 8.
Since the configuration A has a sidestream distillation column, In this configuration, fusel oil is fed into column 1. The bottom
the dividing wall columns (DWC) could be used to achieve high stream (bottom 1) is isoamyl alcohol-rich, and the distillate (dist
purity of the sidestream. Nowadays, several studies have shown 1) goes to a decanter at 25 °C, where there is the formation of an
that DWC represent a very promising technology, allowing a organic phase (organic) and an aqueous solution (aqueous). The
significant energy requirement reduction as well as savings in the second column (column 2) is fed with the organic stream
operating costs.35−37 Dividing wall columns technology has (organic), where this column has the function of recovering the
already been used before for homogeneous and heterogeneous remaining isoamyl alcohol in the bottom stream (bottom 2). The
azeotropic distillations, presenting good results.38−40 Then the final product (bottom) is the sum of the bottom streams from
DWC can be an attractive alternative for the distillation of fusel each column (bottom 1 + bottom 2).
oil. However, preliminary results suggest that it is not possible to Initially a simulation was performed using only the first
eliminate enough water from the distillation column. The DWC column with a reflux ratio of 5.75 and bottom mass flow of
liquid flow rate is lower than in a traditional distillation column, 59 kg/h. By analyzing the results of this simulation, it can be observed
which contributes to smaller equipment and consequently that the bottom stream is a high-purity isoamyl alcohol product
provides a capital saving.41 As this flow is lower, the liquid flow (0.822 in mass fraction). Furthermore, the organic stream
2342 dx.doi.org/10.1021/ie300665z | Ind. Eng. Chem. Res. 2013, 52, 2336−2351
Industrial & Engineering Chemistry Research Article

Figure 8. Flowsheet of configuration B.

Figure 9. Flowsheet of the configuration C.

obtained from the top still had a high concentration of higher in column 2 is more complicated, since the relative volatility of
alcohols including isoamyl alcohol (0.261 in mass fraction), the other higher alcohols and isoamyl alcohol are close to unity,
active amyl alcohol (0.058), isobutanol (0.228), and butanol obtaining a bottom product with a higher content of other higher
(0.021), as well as water (0.123). The purification of this stream alcohols such as isobutanol. From this observation it can be
2343 dx.doi.org/10.1021/ie300665z | Ind. Eng. Chem. Res. 2013, 52, 2336−2351
Industrial & Engineering Chemistry Research Article

Table 2. Results Obtained for the Streams of the Decanter (0.996). In these simulations, both distillations columns
Configuration C operated with reflux ratio of 5.75 and feed at the middle of the
column. It was concluded that with 16 trays the desired content
composition in mass fraction
in the bottom product (bottom) is achieved. The energy con-
components feed aqueous phase organic phase sumed by the reboiler was 3.68 kg steam/kg product.
isoamyl alcohol 0.5570 0.0123 0.6102 It is observed that not only does this configuration present
active amyl alcohol 0.1207 5.30 × 10−05 0.1325 higher energy requirements compared to configuration A, con-
isobutanol 0.0671 0.0049 0.0731 figuration B also includes a second distillation column with a
butanol 0.0057 9.64 × 10−06 0.0063 considerable number of trays, which makes the implementation
pentanol 0.0003 6.80 × 10−06 0.0003 of this proposed configuration impracticable.
propanol 0.0094 0.0010 0.0102 4.5. Configuration C. As discussed earlier, the reduction of
ethanol 0.0866 0.0048 0.0946 water content in the feed stream facilitates the fractionation of
methanol 0.0002 0.0008 0.0002 fusel oil. Therefore, it is necessary to investigate a process capable
water 0.1530 0.9762 0.0726 of substantially removing water from the fusel oil feed stream.
The stream of higher alcohols removed from the bioethanol
mass flow (kg/h) 100 9.92 91.08 rectification column is submitted to a washing process for the
recovery of ethanol which it contains, where the aqueous stream
Table 3. Comparison of the Three Configurations returns to the process and the organic stream is commercialized
config A config B config C as fusel oil. Therefore, fusel oil obtained from the distilleries is
number of columns 1 2 2 found at the solubility limit, and the addition of a small amount of
number of trays 30 30 (column 1) 30 (column) water is sufficient to promote phase separation.
16 (column 2) 3 (stripping The addition of water to the fusel oil induces the formation of
column) two liquid phases, an aqueous phase composed mainly of water
number of decanters 1 1 1 with low concentration of organics, and an organic phase rich in
mass fraction of isoamyl alcohol + 0.996 0.996 0.996 isoamyl alcohol with a reduced water content. In order to avoid
active amyl alcohol in final product that the addition of water to the process results in the loss of
mass fraction of isoamyl alcohol in 0.818 0.818 0.818
final product (IA) higher alcohol in the aqueous stream, an operation is necessary
mass fraction of active amyl alcohol in 0.178 0.178 0.178 for their recovery.
final product Configuration C is illustrated in Figure 9. A decanter was used
recovery of isoamyl alcohol (RE) (%) 99.53 99.53 99.53 at 25 °C receiving 100 kg fusel oil/h and 1 kg water/h. The
specific steam consumption (SSC) 1.1321 3.6800 0.9111 organic stream is fed to a distillation column. Stripping of organics
(kg steam/kg product) (stripping column) was suggested to recover the alcohols present
in the aqueous stream. The aqueous stream from the decanter is
concluded that the mass flow of the bottom product in column 1 fed into this column at the first stage. The higher alcohols are at
must be greater than the mass flow of the bottom product in infinite dilution in this solution in which repulsive attractions
column 2. Thus, it is possible to obtain a final product (bottom prevail, resulting in a considerable increase in volatility of these
1 + bottom 2) with high purity of isoamyl alcohol. compounds. Thus, the higher alcohols are concentrated in the
The bottom product mass flow acquired in column 1 (59 kg/h) vapor phase, which allows for obtaining a stream rich in higher
was the maximum possible while ensuring that liquid phase alcohols in the top of this column and a stream practically free of
separation does not occur inside the column. Therefore, the organics in its bottom.
bottom mass flow of the second column was set at 8.77 kg/h. The The conditions used for the stripping column were three
sum of these two flow rates represents the total mass flow of stages and a reflux ratio of 1. Mass flow of the distillate was varied
isoamyl alcohol and amyl active alcohol fed into the process to obtain a high recovery of isoamyl alcohol in this stream,
(67.77 kg/h). assuming a value of 0.5 kg/h in this simulation, which resulted in
A series of steady-state simulations was performed to deter- 99.26% recovery of isoamyl alcohol present in the aqueous
mine the minimum number of trays in the second distillation stream.
column (column 2) needed to attain the content of isoamyl Constructive and operating conditions used for the distillation
alcohol and active alcohol stipulated for the bottom product column were identical to those obtained in configuration A,

Table 4. Composition of Input and Output Streams of All Configurations

config A config B config C

feed distillate bottom aqueous dist 2 bottom aqueous dist bottom aqueous 2
isoamyl alcohol 0.5570 0.011 0.818 0.003 0.006 0.818 0.012 0.012 0.818 0.096
active amyl alcohol 0.1207 0.067 0.178 1.3 × 10−04 1.2 × 10−04 0.178 0.005 0.223 0.178 0.023
isobutanol 0.0671 0.276 1.9 × 10−04 0.081 0.335 6.1 × 10−04 0.040 0.281 2.1 × 10−04 2.5 × 10−04
butanol 0.0057 0.015 0.003 0.004 0.019 0.003 4.1 × 10−04 0.014 3.5 × 10−03 5.9 × 10−03
pentanol 0.0003 1.1 × 10−03 4.4 × 10−04 2.6 × 10−04 6.2 × 10−05 4.4 × 10−04 9.5 × 10−04 1.6 × 10−07 4.4 × 10−04 1.4 × 10−03
propanol 0.0094 0.040 0.001 9.7 × 10−03 0.046 0.018 0.007 0.039 1.2 × 10−03 0.865
ethanol 0.0866 0.369 2.8 × 10−05 0.082 0.412 0.002 0.081 0.363 3.8 × 10−05 1.4 × 10−03
methanol 0.0002 7.2 × 10−04 1.9 × 10−12 4.4 × 10−04 3.7 × 10−04 3.1 × 10−08 9.5 × 10−04 6.3 × 10−04 1.6 × 10−12 5.2 × 10−04
water 0.1530 0.289 8.6 × 10−13 0.819 0.182 2.7 × 10−08 0.858 0.290 4.0 × 10−13 0.998

2344 dx.doi.org/10.1021/ie300665z | Ind. Eng. Chem. Res. 2013, 52, 2336−2351

Industrial & Engineering Chemistry Research Article

of isoamyl alcohol occurs, whose mass fraction was increased

from 0.5570 to 0.6102.
Using configuration C the established purity was obtained with
99.53% of recovery of isoamyl alcohol and 0.9111 of SSC. The
low value found for the specific steam consumption is
highlighted. This occurs mainly due to the fact that column
operates with a lower total liquid mass flow when compared to
other configurations, resultant of the preremoval of the aqueous
stream in the decanter. Therefore, a lower evaporation rate in the
reboiler is required, reducing the energetic cost.
By analyzing the results, it can be concluded that the stripping
column plays a fundamental role in the recovery of isoamyl
alcohol, since a small number of trays was sufficient to recover the
higher alcohols in the top of the column.
4.6. Economic Comparison between Configurations A,
B, and C. Table 3 presents the equipments involved in each
proposal along with the main results, Table 4 shows the
composition results, and Figure 10 provides the operating
conditions for all configurations. It is observed that in all con-
figurations the active amyl alcohol composition in the final product
is similar, which ensures the same proportion of the isomers isoamyl
alcohol and active amyl alcohol. Active amyl alcohol is recovered
mostly in the bottom stream, with recovery of 99.99% in the three
proposed configurations. Configuration C was the most
energetically efficient configuration. In relation to the amount
of equipment, this proposal also seems to be the most viable.
In order to evaluate the cost of these three configurations, an
economic analysis was also performed as part of this study. The
same operating conditions (input, outputs, cooling water
temperature, and steam conditions) were used in all config-
urations. Total annual cost (TAC) was calculated in order to
perform a comparison of the three configurations, where the
TAC includes the annualized capital costs and the operating
costs. Estimation of equipment costs are based on the procedure
of Douglas,42 including column shells, internal trays of the
column, and also the reboiler and condenser. Details for the
economic basis used in the calculations are based on the study by
Luyben43 and are given in Table 5. The payback period was

Table 5. Basis of Economics and Equipment Sizing

diameter: Aspen tray sizing
length: number of trays with 0.61 m spacing plus 20% extra length
heat-transfer coefficient (Uc) = 0.852 kW·K−1·m−2
differential temperature (ΔTc) = reflux-drum temperature − 310 K
condenser area (m2) = condenser duty/(UcΔTc)
heat-transfer coefficient (Ur) = 0.568 kW·K−1·m−2
differential temperature (ΔTr) = 424.25 − base temperature
Figure 10. Operating conditions for configurations A, B, and C. reboiler area (m2) = reboiler duty/(UrΔTr)
utilities cost
LP steam $13.28/GJ
except for the reflux ratio, which was 2.6 (the minimum value
cooling water $0.354/GJ
necessary to achieve the mass fraction of 0.996 of isoamyl alcohol
TAC = (capital cost/payback period) + operating cost
and active amyl alcohol in the product stream). The stream of
payback period = 3 years
recovered organics was fed in the middle of the main column
Marshall and Swift index45 = 1448.3
(stage 16).
Table 2 shows the result for the input and output streams of
the decanter. Starting with a feed containing 0.1530 of water in assumed to be 3 years. Additionally, unit costs of low-pressure
mass fraction and utilizing the decantation process proposed, it steam and cooling water were assumed as 13.28 and 0.354 $/GJ,
was possible to obtain a column feed stream with a water com- respectfully, according to Turton et al.44 The TAC for the three
position of 0.0726. It was also observed that a preconcentration configurations are compared in Table 6.
2345 dx.doi.org/10.1021/ie300665z | Ind. Eng. Chem. Res. 2013, 52, 2336−2351
Industrial & Engineering Chemistry Research Article

Table 6. TAC Comparison of Configurations

config A config B config C
col 1 col 1 col 2 col stripping col
column shell cost ($) 60865.06 98004.99 31635.94 53194.71 974.81
column trays cost ($) 1632.65 3263.65 699.89 1342.25 5.87
condenser cost ($) 11815.27 25259.02 13098.67 11429.40 726.85
reboiler cost ($) 43576.24 78181.19 37040.83 36703.70 2307.34
steam cost ($/year) 18826.76 46045.13 15093.74 14634.86 516.10
cooling water cost ($/year) 320.18 1097.38 371.29 304.87 4.90
total annualized capital cost ($/year) 39296.41 68236.28 27491.78 34223.35 1338.29
total annualized operating cost ($/year) 19146.93 47142.50 15465.03 14939.73 521.00
TAC ($1000/year) 58.44 158.34 51.02

As expected, configuration B presents the largest TAC value Table 7. Composition of Input and Output Streams of
since the presence of two columns causes an obvious increase in Optimal Configuration C
capital cost as well as an increase in operating cost. Configuration
feed distillate bottom aqueous
C has the least TAC, being 12.7% less than configuration A. The
main reason for the lower TAC is because of the capital saving in isoamyl alcohol 0.5570 0.010 0.818 9.6 × 10−05
active amyl alcohol 0.1207 2.7 × 10−06 0.178 2.3 × 10−06
the main column of this configuration. As previously mentioned,
isobutanol 0.0671 0.281 1.4 × 10−04 2.5 × 10−04
this column operates with a lower total liquid mass flow, resulting
butanol 0.0057 0.015 0.003 5.9 × 10−07
in a column with smaller diameter, which consequently requires pentanol 0.0003 6.3 × 10−08 4.4 × 10−04 1.4 × 10−07
less capital investment. The lower total liquid mass flow also propanol 0.0094 0.039 3.4 × 10−08 8.6 × 10−05
directly affects the heat duties of the process. As a result, the TAC ethanol 0.0866 0.363 2.7 × 10−10 1.4 × 10−03
of configuration C is lowest. methanol 0.0002 6.3 × 10−04 6.6 × 10−19 5.2 × 10−04
Among the three configurations, configuration C was the most water 0.1530 0.290 2.1 × 10−20 0.998
economically advantageous, and therefore a procedure was used
to achieve an improved design for further reducing its TAC. streams. Results for the mass flows are the same as shown in
4.7. Optimal Design of Configuration C. Total annual Figure 10.
cost (TAC) is used as the economic parameter to be minimized In the next section, a plant-wide control system is developed and
for configuration C. The design variable was the number of trays tested for configuration C with the aforementioned specifications.
and the reflux ratio the manipulating variable. The reflux ratio of
the column was adjusted to obtain a product with a minimum 5. PROCESS DYNAMICS AND CONTROL
composition of 0.996 in mass fraction of the two alcohols, The proper overall control strategy for configuration C was
isoamyl alcohol and active amyl alcohol. All simulations are investigated. The Aspen Plus steady-state simulation was
carried out using the same specification: the bottom mass flow of exported to the dynamic simulation of Aspen Dynamics.
the column was fixed at 67.77 kg/h with feed in its middle. The Volumes of the column bases were specified with a holdup
stripping column with three trays operates with distillate mass time of 10 min and 50% liquid level. The decanter was sized for a
flow of 0.5 kg/h and reflux ratio of 1. 20 min holdup to allow for the two liquid phases to separate.
Figure 11 shows the results of the TAC for some simulations 5.1. Selection of Temperature Control Trays. The slope
performed when varying the number of trays from 25 to 80. It can criterion analysis was used to determine the tray temperature
control points. Figure 12 shows the difference between
temperatures on adjacent trays for the column and stripping
column. There is a large change at the feed stage (stage 22) of the
column; however, the feed is not a good location for temperature
control.43 A large change in temperature is also observed in stage
11, which was selected for temperature control of the column.
The slope analysis suggests the use of stage 3 for temperature
control of the stripping column.
5.2. Control Structure. Figure 13 shows the control
structure developed for configuration C consisting of eight
inventory control loops (six levels and two pressures). In each
column the reflux drum level is controlled by manipulating the
distillate flow, and the column bottom level is controlled by
manipulating the bottom flow. In the decanter, the aqueous
phase level is controlled by manipulating the aqueous outlet flow,
and the organic phase level is controlled by manipulating the
Figure 11. Effect of the number of stage on TAC’s. organic outlet flow. Top pressures of the two columns are con-
trolled by manipulating the condenser duties. All level controllers
are proportional only with a gain of 2.
be observed that the number of stages equal to 40 corresponds to The temperature of one tray in each column was controlled by
the minimum TAC. In this simulation the reflux ratio was 1.3 and manipulating the reboiler heat input in that column. A 1 min
SSC = 0.66. Table 7 shows the results for the input and output dead time is inserted in each temperature loop. Relay-feedback
2346 dx.doi.org/10.1021/ie300665z | Ind. Eng. Chem. Res. 2013, 52, 2336−2351
Industrial & Engineering Chemistry Research Article

Figure 12. Configuration C temperature profile and slope: (A) column and (B) stripping column.

Figure 13. Proposed overall control strategy.

tests and Tyreus−Luyben tuning were used to obtain controller tuning constants for the third stage temperature loop of the
tuning parameters in the column temperature loops. The striping column are Kc = 10.12 and τI = 7.92 min.
resulting PI tuning constants for the 11th stage temperature The reflux ratio is held constant, but the reflux flow can still be
loop of the column are Kc = 6.41 and τI = 15.84 min, and the adjusted in the case of feed composition disturbances.
2347 dx.doi.org/10.1021/ie300665z | Ind. Eng. Chem. Res. 2013, 52, 2336−2351
Industrial & Engineering Chemistry Research Article

Figure 14. Responses with feed flow changes (solid line, −20%; dashed line, +20%).

5.3. Dynamic Performance Results. To evaluate the controlled back to their set point values within 2 h, and the
control performance of this control structure, disturbances in compositions of isoamyl alcohol and active amyl alcohol in the
feed flow rate and feed composition are made at time = 1 h. product are held quite close to the desired values. It is also
Figure 14 shows the dynamic responses for ±20% feed flow rate noticed that the bottom mass flow of the column decreases or
changes. It is observed that the two tray temperatures are increases correspondingly with the changes in the isoamyl
2348 dx.doi.org/10.1021/ie300665z | Ind. Eng. Chem. Res. 2013, 52, 2336−2351
Industrial & Engineering Chemistry Research Article

Figure 15. Responses with feed composition changes (solid line, −10% of isoamyl alcohol and active amyl alcohol; dashed line, +10% of isoamyl alcohol
and active amyl alcohol).

alcohol and active amyl alcohol feed composition, maintaining active amyl alcohol concentrations by ±10%, with the others
high recoveries. seven components retaining their in initial ratios to each other.
Figure 15 provides the results for changes in the feed The two tray temperatures were again controlled back to their set
composition by increasing or decreasing the isoamyl alcohol and point values. A small decrease in purity of the bottom product is
2349 dx.doi.org/10.1021/ie300665z | Ind. Eng. Chem. Res. 2013, 52, 2336−2351
Industrial & Engineering Chemistry Research Article

noticed with the composition disturbance of −10%. The bottom (9) Pérez, E. R.; Cardoso, D. R.; Franco, D. W. Análise dos álcoois,
outlet mass fraction of isoamyl alcohol and active amyl alcohol ́
ésteres e compostos carbonilicos em amostras de óleo fúsel. Quim. Nova
deviated from 0.996 to 0.994. This occurs because with the 2001, 24, 10 [in Portuguese].
decrease of isoamyl alcohol and active amyl alcohol in feed there (10) Aucejo, A.; Burguet, M. C.; Montón, J. B.; Muñoz, R.; Sanchotello,
M.; Vázquez, M. I. Vapor−liquid-equilibria for systems of 1-butanol with
was a parallel increase in other higher alcohols such as butanol
2-methyl-1-butanol, 3-methyl-1-butanol, 2-methyl-2-butanol, and 3-
and isobutanol, thus resulting in an increase of these two alcohols methyl-2-butanol at 30 and 100 kPa. J. Chem. Eng. Data 1994, 39, 271.
in the final product and decreasing purity of the desired isoamyl (11) Aucejo, A.; Burguet, M. C.; Montón, J. B.; Muñoz, R.; Sanchotello,
alcohol. M.; Vázquez, M. I. Isothermal vapor−liquid-equilibria of 1-pentanol
These simulation results demonstrate that the proposed con- with 2-methyl-1-butanol, 2-methyl-2-butanol, and 3-methyl-2-butanol.
trol structure provides effective control for different disturbances. J. Chem. Eng. Data 1994, 39, 578.
(12) Brunjes, A. S.; Bogart, M. J. P. Vapor−liquid equilibria for
6. CONCLUSIONS commercially important systems of organic solvents: The binary systems
ethanol−n-butanol, acetone−water and isopropanol−water. Ind.
All proposed processes were capable of obtaining high-purity Eng.Chem. 1943, 35, 255.
isoamyl alcohol and active amyl alcohol products with high (13) Cho, T. H.; Ochi, K.; Kojima, K. Isobaric vapor−liquid-equilibria
recovery, but the total annual cost of configuration C is less than for binary S-systems with limited miscibility, water−normal-amyl
the others. The results show that it is not possible to obtain only alcohol and water−isoamyl alcohol. Kagaku Kogaku Ronbun 1984, 10,
isoamyl alcohol by conventional distillation processes of fusel oil; 181.
thus, a product is obtained consisting of a mixture of the isomers (14) Gmehling, J.; Onken, U. Vapor−liquid equilibrium data
active amyl and isoamyl alcohols. An overall control strategy of collection. In DECHEMA Chemistry Data Series; Behrens, D.,
this configuration was proposed, and a control performance can Eckermann, R., Eds.; DECHEMA: Frankfurt, Germany, 1981.
be obtained using simple temperature control. The results (15) Hellwig, L. R.; Winkle, M. V. Vapor−liquid equilibria for ethyl
presented in this work for configuration C provide support for alcohol binary systems. Ind. Eng.Chem. 1953, 45, 624.
development for fusel oil industrial purification plants to obtain (16) Hill, W. D.; Winkle, M. V. Vapor−liquid equilibria in methanol
binary systems: Methanol−propanol, methanol−butanol, and meth-
the isoamyl alcohol. Configuration C presents an additional anol−pentanol. Ind. Eng.Chem. 1952, 44, 205.
advantage compared to the conventional distillation process, (17) Kurihara, K.; Nakamichi, M.; Kojima, K. Isobaric vapor−liquid
since reduced water content in the column feed stream results in equilibria for methanol + ethanol + water and the three constituent
a lower energy requirement.

binary systems. J. Chem. Eng. Data 1993, 38, 446.
(18) Lladosa, E.; Montón, J. B.; Burguet, M. C.; Muñoz, R. Vapor−
AUTHOR INFORMATION liquid equilibria in the ternary system dipropyl ether plus 1-propanol
Corresponding Author plus 1-pentanol and the binary systems dipropyl ether plus 1-pentanol,
1-propanol plus 1-pentanol at 101.3 kPa. Fluid Phase Equilib. 2006, 247,
*Fax: +55 19 3521 4027. E-mail: eacbat@fea.unicamp.br.
Notes (19) Mohsen-nia, M.; Memarzadeh, M. R. Isobaric (vapour plus liquid)
The authors declare no competing financial interest. equilibria for the (1-propanol+1-butanol) binary mixture at (53.3 and

The authors are grateful to CNPq (131859/2010-2) and
91.3) kPa. J. Chem. Thermodyn. 2010, 42, 792.
(20) Resa, J. M.; González, C.; Moradillo, B.; Ruiz, A. Isobaric vapor−
liquid equilibria of 3-methyl-1-butanol with methanol and vinyl acetate
at 101.3 kPa. Fluid Phase Equilib. 1997, 132, 205.
FAPESP (08/56258-8) for the financial support.

(21) Resa, J. M.; González, C.; Goenaga, J. M.; Iglesias, M. Density,
refractive index, and speed of sound at 298.15 K and vapor-liquid
REFERENCES equilibria at 101.3 kPa for binary mixtures of ethyl acetate+1-pentanol
(1) Patil, A. G.; Koolwal, S. M.; Butala, H. D. Fusel oil: Composition, and ethanol+2-methyl-1-propanol. J. Chem. Eng. Data 2004, 49, 804.
removal and potential utilization. Int. Sugar J. 2002, 104, 51. (22) Resa, J. M.; González, C.; Goenaga, J. M. Density, refractive index,
(2) Batista, F. R. M.; Meirelles, A. J. A. Computer simulation applied to speed of sound at 298.15 K, and vapor−liquid equilibria at 101.3 kPa for
studying continuous spirit distillation and product quality control. Food binary mixtures of methanol plus 2-methyl-1-butanol and ethanol plus
Control. 2011, 22, 1592. 2-methyl-1-butanol. J. Chem. Eng. Data 2005, 50, 1570.
(3) Vauclair, C.; Tarjus, H.; Schaetzel, P. Permselective properties of (23) Resa, J. M.; Goenaga, J. M.; Iglesias, M. Vapor−liquid equilibria at
PVA−PAA blended membrane used for dehydration of fusel oil by 101.3 kPa for binary mixtures containing 2-methyl-1-propanol+2-
pervaporation. J. Membr. Sci. 1997, 125, 293. methyl-1-butanol, 2-methyl-1-propanol+3-methyl-1-butanol, and 2-
(4) Luyben, W. L.; Chien, I. L. Design and Control of Distillation Systems methyl-1-propanol+1-pentanol. J. Chem. Eng. Data 2006, 51, 1892.
for Separating Azeotropes; John Wiley & Sons, Inc.: Hoboken, NJ, 2010. (24) Resa, J. M.; González, C.; Goenaga, J. M. Density, refractive index,
(5) Dörmő , N.; Bélafi-Bakó, K.; Bartha, L.; Ehrenstein, U.; Gubicza, L. speed of sound at 298.15 K, and vapor−liquid equilibria at 101.3 kPa for
Manufacture of an environmental-safe biolubricant from fusel oil by binary mixtures of propanol+2-methyl-1-butanol and propanol+3-
enzymatic esterification in solvent-free system. Biochem. Eng. J. 2004, 21, methyl-1-butanol. J. Chem. Eng. Data 2006, 51, 73.
229. (25) Tamir, A.; Wisniak, J. Binary vapor−liquid equilibria of some amyl
(6) Güvenç, A.; Kapucu, N.; Kapucu, H.; Aydoğan, Ö .; Mehmetoğlu, alcohols. J. Chem. Eng. Data 1976, 21, 182.
Ü . Enzymatic esterification of isoamyl alcohol obtained from fusel oil: (26) Thiede, S.; Horstmann, S.; Meisel, T.; Sinnema, J.; Gmehling, J.
Optimization by response surface methodology. Enzyme Microb. Experimental determination of vapor−liquid equilibria and excess
Technol. 2007, 40, 778. enthalpy data for the binary system 2-methyl-1-butanol+3-methyl-1-
(7) Nemestóthy, N.; Gubicza, L.; Fehér, E.; Bélafi-Bakó, K. butanol as a test mixture for distillation columns. Ind. Eng. Chem. Res.
Biotechnological utilisation of fusel oil, a food industry by-product: A 2010, 49, 1844.
kinetic model on enzymatic esterification of i-amyl alcohol and oleic acid (27) Wisniak, J.; Tamir, A. Association effects in the methanol−1-
by Candida antarctica lipase B. Food Technol. Biotechnol. 2008, 46, 44. pentanol system. J. Chem. Eng. Data 1988, 33, 432.
(8) Ö zgülsün, A.; Karaosmanôglu, F.; Tüter, M. Esterification reaction (28) Bessa, L. C. B. A.; Batista, F. R. M.; Meirelles, A. J. A. Double-effect
of oleic acid with a fusel oil fraction for production of lubricating oil. J. integration of multicomponent alcoholic distillation columns. Energy
Am. Oil Chem. Soc. 2000, 77, 105. 2012, 45, 603.

2350 dx.doi.org/10.1021/ie300665z | Ind. Eng. Chem. Res. 2013, 52, 2336−2351

Industrial & Engineering Chemistry Research Article

(29) Kadir, S.; Decloux, M.; Giampaoli, P.; Joulia, X. Liquid−liquid

equilibria of the ternary systems 3-methyl-1-butanol + ethanol plus
water and 2-methyl-1-propanol + ethanol + water at 293.15 K. J. Chem.
Eng. Data 2008, 53, 910.
(30) Ghizellaoui, S.; Coquelet, C.; Richon, D.; Meniai, A. H. Liquid−
liquid equilibrium of (water + 1-propanol + 1-pentanol) system at
298.15 and 323.15 K. Fluid Phase Equilib. 2010, 296, 42.
(31) Gomis-Yagües, V.; Ruíz-Bevià, F.; Ramos-Nofuentes, M.;
Fernández-Torres, M. J. The influence of the temperature on the
liquid−liquid equilibrium of the ternary system 1-butanol−1-propanol−
water. Fluid Phase Equilib. 1998, 149, 139.
(32) Sørensen, J. M.; Arlt, W. Liquid−liquid equilibrium data
collection. In DECHEMA Chemistry Data Series; Behrens, D.,
Eckermann, R., Eds.; DECHEMA: Frankfurt, Germany, 1980.
(33) Reid, R. C.; Prausnitz, J. M.; Poling, B. E. The Properties of Gases
and Liquids, 4th ed.; McGraw-Hill Book Co.: New York, 1987.
(34) Liu, Y.; Gao, H.; Sun, J.; Wang, Y.; Wu, P.; Liu, Y. E; Ji, Y. Novel
packing-enhanced distillation separation of isoamyl alcohol isomer:
Experimental and pilot scale study. AIChE J. 2011, 57, 3037.
(35) Asprion, N.; Kaibel, G. Dividing wall columns: Fundamentals and
recent advances. Chem. Eng. Process. 2010, 49, 139.
(36) Dejanović, I.; Matijašević, Lj.; Olujić, Ž . Dividing wall columnA
breakthrough towards sustainable distilling. Chem. Eng. Process. 2010,
49, 559.
(37) Yildirim, Ö .; Kiss, A. A.; Kenig, E. Y. Dividing wall columns in
chemical process industry: A review on current activities. Sep. Purif.
Technol. 2011, 80, 403.
(38) Wang, S.-J.; Lee, C.-J.; Jang, S.-S.; Shieh, S.-S. Plant-wide design
and control of acetic acid dehydration system via heterogeneous
azeotropic distillation and divided wall distillation. J. Process Control
2008, 18, 45.
(39) Kiss, A. A.; Suszwalak, D. J-.P. C. Enhanced bioethanol
dehydration by extractive and azeotropic distillation in dividing-wall
columns. Sep. Purif. Technol. 2012, 86, 70.
(40) Sun, L.-Y.; Chang, X.-W.; Qi, C.-X.; Li, Q.-S. Implementation of
ethanol dehydration using dividing-wall heterogeneous azeotropic
distillation column. Sep. Sci. Technol. 2011, 46, 1365.
(41) Olujic, Z.; Jödecke, M.; Shilkin, A.; Schuch, G.; Kaibel, B.
Equipment improvement trends in distillation. Chem. Eng. Process. 2009,
48, 1089.
(42) Douglas, J. M. Conceptual Design of Chemical Process; McGraw-
Hill: Boston, 1988.
(43) Luyben, W. L. Distillation Design and Control Using Aspen
Simulation; John Wiley & Sons, Inc.: New York, 2006.
(44) Turton, R.; Bailie, R. C.; Whiting, W. B.; Shaeiwitz, J. A. Analysis,
Synthesis, and Design of Chemical Processes, 3rd ed.; Pearson Education:
Boston, 2009.
(45) Chemical Engineering, Economic Indicators, www.che.com.
Accessed July 2012.

2351 dx.doi.org/10.1021/ie300665z | Ind. Eng. Chem. Res. 2013, 52, 2336−2351