Full Paper

Separation of tert-Butyl Alcohol–Water Mixtures by a

Heterogeneous Azeotropic Batch Distillation Process
By Xu Songlin* and Wand Huiyuan

DOI: 10.1002/ceat.200500245

Tert-butyl alcohol and water form an azeotrope at normal pressure. Simple distillation cannot be used to separate these two
components. In this article, a systematic study of the separation of tert-butyl alcohol–water mixtures with an entrainer by
heterogeneous azeotropic batch distillation was performed. Based upon the thermodynamic behavior of the ternary mixtures,
cyclohexane was chosen as the entrainer. It formed ternary and binary heterogeneous azeotropes with the original compo-
nents. The process feasibility analysis was validated by using rigorous simulation with chemical process simulation software –
HYSYS Plant 2.2 and DISTIL 4.1. Simulation results were then corroborated in a batch experimental column for the selected
entrainer.

1 Introduction required for synthesis and retrofit design of separation pro-

The separation of azeotropes and close-boiling mixtures is
often necessary in the pharmaceutical and special chemical
industries. Batch distillation is a common solvent recovery
unit operation and deals with increasing economic incentives
and environmental regulations. Usually a feasible entrainer
is added to the column to break the azeotropes. When the
entrainer is high boiling and is added continuously in the top
section of the batch column, the process is called extractive
batch distillation. When the entrainer forms a homoazeo-
trope or heteroazeotrope with at least one of the original
components and is added batchwise to the original mixture,
the process is called homoazeotropic or heteroazeotropic
batch distillation.
Design and synthesis tools for heterogeneous distillation
were first introduced by Pham and Doherty [1–3]. They
showed that synthesis of heterogeneous continuous distilla-
tion processes for the separation of non-ideal mixtures using
a heterogeneous entrainer involves the analysis of residue
curve maps. It can first be used to select feasible entrainers,
and then to establish the associated distillation column
sequence. Then process parameter optimal values are
looked at, but they depend on the entrainer choice because
this largely determines the azeotropic distillation process
efficiency.
Rodriguez, Gerbaud, and Joulia [4] described the rules for
the selection of a heterogeneous entrainer leading to a feasi-
ble process for the separation of a minimum or maximum
temperature azeotropic binary mixture or a close boiling
binary mixture. Stichmair has done a lot of work on batch
distillation [5, 6]. He used mixed-integer nonlinear program-
ming (MINLP) [7, 8] to design and optimize azeotropic dis-
tillation. This approach can reduce the effort and time
–
[*] X. Songlin (author to whom correspondence should be addressed,
slxu@tju.edu.cn), W. Huiyuan, Department of Pharmaceutical Engineer-
ing, Tianjin University, Tianjin 30072, PR China.
cesses. The model also includes the implementation of cost
correlations for an economic optimization of the complex
process.
Szanyi [9] studied the separation of two non-ideal quater-
nary mixtures containing one azeotropic forming component
based on optimization of the separation structures. The
economic optimization of the different separation structures
results in the conclusion that the heuristic rule for ideal
mixtures, that is, “easy separation first should be done and
the complicated one should be made last”, is valid also
for such non-ideal mixtures. Rodriguez-Donis [10] gave
three examples based on the separation of non-ideal azeo-
tropic or close boiling point binary mixtures through hetero-
geneous batch distillation, which were simulated using a
commercial batch distillation package. Experiments validate
the simulated separation of a minimum boiling azeotropic
mixture.
A novel multi-vessel batch distillation hybrid [11] for
simultaneous separation of ternary heterogeneous azeotro-
pic mixtures was investigated both theoretically and by sim-
ulations by Skouras and Skogestad. The novel process is sim-
ple and practical. The closed mode of operation requires
minimum operator intervention and monitoring. The col-
umn runs by itself and the products are accumulated in the
vessels during the process. Two pure components are always
recovered in the vessels, and an aqueous phase rich in the
third component (water) is recovered in the decanter. The
feasibility analysis [12] was also done for both the conven-
tional batch rectifier and the multi-vessel batch column.
Warter did some experiments [13] for the separation of zeo-
tropic and azeotropic mixtures using a batch distillation
column with a middle vessel.
The aim of this paper is to study the performance of
heterogeneous batch distillation for the refining of tert-butyl
alcohol. The anhydrous tert-butyl alcohol (99 %) is often
used in pharmaceutical industries for producing artificial
musk, essence, and raw medicine. Grane et al. [14] first stud-
ied the purification of tert-butyl alcohol. Isobutane is oxi-

Chem. Eng. Technol. 2006, 29, No. 1 © 2006 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim 113
 Full Paper

dized to provide a debutanized oxidate comprising tertiary Table 2. The binary interaction parameters for the NRTL model.
butyl alcohol, acetone, water and other byproducts, includ-
TBA Water Cyclohexane
ing high boiling products. Water is removed by extractive
TBA – 2304.09200 155.27960
distillation using a combination of water and xylene as the
extractant. The molar amount of recycled water is more than Water 828.81620 – 3678.01439
that of water to be removed from the oxidant. Berg and Cyclohexane 459.87130 4332.90898 –
Yang [15] investigated typical effective agents; for azeotro-
pic distillation: vinyl n-butyl ether and propylene glycol
dimethyl ether; by extractive distillation: 1, 3-butanediol and
triethylene glycol.

2 Selection of a Suitable Entrainer for the

Separation of a tert-Butyl Alcohol Azeotropic
Mixture

Liquid-vapor equilibrium data for the binary mixture have

been reported in the scientific literature. A minimum boiling
temperature azeotrope with a weight fraction of tert-butyl
alcohol equal to 0.8824 and a temperature of 79.91 °C at
101.3 KPa is reported. The candidate homogeneous and het-
erogeneous entrainers are investigated applying the rules
reported by Rodriguez et al. [4, 16]. The existence of binary
and ternary azeotropes was sought by using literature data,
however no homogeneous entrainer matching the reported
rules has been found, though some suitable heterogeneous Figure 1. Residue curve maps of ternary systems TBA–water–cyclohexane.
entrainers have been identified. Cyclohexane was finally
chosen as the entrainer. The temperature and composition
of the azeotropic mixtures with the original components are
displayed in Tab. 1. 3 Simulation of the Separation of the Mixture
The NRTL model is used to predict the activity coeffi- by Heteroazeotropic Batch Distillation using
cients, and the ideal gas model for the fugacity coefficient. Cyclohexane
The binary interaction parameters for the NRTL model and
the residue curve map of the ternary systems are shown in The separation of a TBA–water mixture is studied by
Tab. 2 and Fig. 1, respectively. The binary interaction pa- using cyclohexane as the entrainer. The simulation of the
rameters of TBA–water are from the “vapor-liquid equilibri- process is performed with the chemical process simulation
um data collection” [17], the interaction parameters of software – HYSYS. Plant 2.2. The HYSYS dynamic model
TBA–cyclohexane are from the Hyprotech Internal Data- shares the same physical property packages as the steady
base, while those for cyclohexane–water are estimated using state model. The dynamic analysis of a process can provide
Standard UNIFAC VLE formulation. more information than steady state modeling alone.

Table 1. The temperatures and compositions of the azeotropic mixtures.

Azeotropic mixtures Azeotropic Composition of the azeotropic mixture [wt %]

temperature
[°C] TBA Water Cyclohexane

TBA-water-cyclohexane 65 21 8 71

Cyclohexane-water 68.95 0 8.4 91.6

Cyclohexane-TBA 71.3 37 0 63

TBA-water 79.91 88.24 11.76 0

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The column configuration is shown in Fig. 2, while the
technical features and operating conditions are shown in
Tab. 3. The column model consists of the usual tray by tray
MESH equations which are solved for the whole column de-
canter, taking into account the liquid-liquid de-mixing. The
simulation aspects are summarized below:
– The column contains a partial condenser, a reboiler, and
forty five theoretically perfect plates.
– The liquid percent level in the condenser is managed by a
PID controller connected to the organic reflux and the set
point is 40 %.
– The simulation does not consider the full reflux step, and
begins at the distillate removal step. The initialization of
the column is defined by the steady state value.
– Because in the full reflux step we can draw a great deal of
water from the decanter, this part of water is ignored. The
initial water mole fraction is lower in the simulation than
that in the true material. The initial composition (mole) is
0.5467/0.1563/0.2970 (TBA/water/cyclohexane).
– The initial liquid percent levels in the condenser and
reboiler are 0 % and 60 %, respectively.
Figure 2. The column configuration. 1 – cyclohexane, 2 – TBA, 3 – water.
Table 3. The column technical features and operating conditions.
Parameters Value
Packing Correlation Rabbins
Packing Type Ballast Rings (metal)
1 inch
Section Diameter [m] 0.9144
6
Reboiler Duty [kJ/h] 3.909·10
6
Condenser Duty [kJ/h] –3.653·10
Condenser Volume [m3] 4.5
Chem. Eng. Technol. 2006, 29, No. 1 © 2006 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim
Full Paper
The simulation results are shown in Figs. 3–5. As we can
see, the distillate component did not change much at the be-
ginning of 2.5 h and the water mass fraction remained stea-
dy. The cyclohexane component decreased appreciably in
the middle of the procedure, while the TBA increased. The
liquid percent level of the reboiler was higher than 60 % in
the beginning, because the column had liquid holdup when
the simulation started. The liquid in the column fell into the
reboiler as the initial heat didn’t produce enough vapor to
prevent the liquid from dropping. Then reboiler level de-
creased sharply while the condenser level increased, which
illustrated the unsteadiness in the start up of the batch distil-
lation process. The TBA component in the reboiler reached
99 % at about 75 min, but the distillate did not achieve the
quality requirement. The product can be drawn from the
reboiler in theory.
In the actual process, heating of the product would be con-
tinued and it would be drawn from the tower top. At about
160 min, the cyclohexane in the column was almost removed
from the system and its mass fraction in the distillate
deceased sharply to 0.008, while the TBA reached 0.99.
Parameters Value
HETP[m] 0.4965
X-Sectional Area [m2] 0.6567
Section Height [m] 22.34
Distillate Flow Rate [kg/h] 1000
Vapor Flow Rate [kg/h] 0
Reboiler volume [m3] 10
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At the same time, little liquid remained in the reboiler and

the main product was in the condenser. The output of ac-
ceptable product was about 1790 kg and the TBA recovery
was 63.27 %. The distillate removed before achieving the
required quality can be collected in a decanter and left it
standing to de-mix. The organic substance may then be
reclaimed in the next batch distillation process.

4 Experimental Results of the Heteroazeotropic

Batch Distillation

4.1 Materials

The component mass fraction of TBA–water raw material

is 0.8597/0.1293/0.0121 (TBA/water/other heavy impurity).
Figure 3. Component mass fraction of the distillate. 1 – TBA, 2 – water, The purity of cyclohexane is 0.995 (mass fraction).
3 – cyclohexane.

4.2 Equipment

Batch experiments are carried out in a small laboratory

column to evaluate the relevancy of the synthesis and simu-
lation achieved so far. The technical features of the column
and the operating conditions are similar for the experiments
and the simulations. The glass column has a total height of
1.5 m and an internal diameter of 0.03 m. It is packed with
stainless steel h-rings of 3 mm by 3 mm. The total packed
height is about forty five theoretical plates and the total
liquid hold is above 45 mL. The bottom is a 250 mL flask.
In the experiment a condenser with a special structure was
used, which has a mini decanter above the sample connec-
tion. The sketch map is shown in Fig. 6. The vapor stream
forms two liquid phases after condensation in the decanter.

Figure 4. Liquid percent level in the condenser and reboiler. 1 – condenser,

2 – reboiler.

Figure 6. The special condenser in the experiment. 1 – thermometer, 2 – the

exit of condensate water, 3 – the entrance of condensate water, 4 – controller
Figure 5. Liquid mole fraction in the reboiler. 1 – reboiler, 2 – condenser. of reflux ratio, 5 – decanter, 6 – sample connection.

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The organic phase will be refluxed back to the distillation

column to provide enough entrainer inside the column. The
aqueous phase containing mostly water will be drawn out
from the system before the phase boundary surface is above
the reflux entrance. The reflux ratio is provided at the top of
the column by a solenoid valve.

4.3 Experimental Procedure

60 mL cyclohexane and 120 mL original aqueous tert-

butyl alcohol mixture were charged into the bottom. Then it
was heated and kept at total reflux for 2 h. The condenser is
subcooled to 28 °C. The power for the boiler heating is
200 W. During the total reflux, the water phase is accumu-
lated in the decanter, so it can be drawn out from the system
whenever necessary. After the total reflux, the distillate was Figure 7. Comparison between experimental and simulation results for the
temperature in the reboiler/condenser. 1 – reboiler, 2 – condenser.
removed at a reflux ratio of 3. Before the top temperature
reached 80 °C, the removed distillate was collected in a bea-
ker and left to de-mix for a while. The organic phase that
contains entrainer and tert-butyl alcohol may be recycled in
a later distillation process. Analysis of the distillate composi-
tion was performed about every 15 min. The temperatures
of the top and the bottom of the column were recorded
every 10 min.

4.4 Experimental Results

The TBA, cyclohexane, and other high boiling organic

impurity compositions were determined using a GC-9A gas
chromatograph with a FID detector and with a column HP-
5ms (30 m × 0.32 mm). The injector and detector tempera-
ture were held at 250 °C while the column temperature was
set to 50 °C. The water composition was determined using
the same gas chromatograph with a TCD detector and with
a GDX-103 column. The TCD electric current was 75 mA
and the column temperature 200 °C.
The temperature and composition of the distillate stream
during the process vs. simulation results are shown in Figs. 7
and 8. The simulation began after the stage of total reflux, so
the curves begin at 120 min in the figures.
From Figs. 7 and 8 we can see that the experimental and
simulation results are in good agreement and that no major
discrepancy is noticed, even though the simulation is based
on numerous assumptions such as constant molar holdup in
the column, omission of fluid-dynamics, no heat losses over
the column, and no sub-cooling at the condenser. The fol-
lowing remarks are made:
– Experimental and simulated temperatures in the reboiler
and condenser exhibit the same trend after equivalent
duration. The curve of the reboiler temperature is a little
smoother in the simulation than that in the experiment.
The final temperature of the reboiler in the experiment is
higher than the simulation results. This may due to the oc-
currence of some high boiling organic impurities in the
Figure 8. Comparison between experimental and simulation results for the
TBA concentration in the distillate.
TBA raw feed; at the end of the experiment these impuri-
ties remained in the bottom. The boiling point is higher
than TBA. In addition, the top temperature in the experi-
ment is lower than the simulation result, because the ther-
mometer in the condenser is located in a glass cover and
doesn’t touch the vapor from the column directly. There
will cause ∼1–2 °C difference from the actual temperature.
– The TBA recovery is about 52 % in the experiment. The
trend of the TBA mass fraction in distillate is almost the
same as the one in the simulation result, but the product
purity and recovery are lower than the simulation results.
In particular, the initial product purity has a large differ-
ence between the simulation results. The main reason is
that we can’t estimate the quantity of water drawn out
during the full reflux step accurately. The water composi-
tion in the experimental material is higher than in simula-
tion. The column has some liquid holdup when the simula-
tion begins, which also cause the product purity and TBA
recovery to be higher.

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 Full Paper
– The change of top product from TBA-water-cyclohexane
ternary azeotropic mixture to high-purity TBA is also
shown in Figs. 7 and 8. The slope is larger in the simula-
tion curves than that in the experimental curves. This dem-
onstrates there are differences between the theory and
experiment. In the actual process this change will not take
place within several minutes.
5 Conclusions
Cyclohexane was chosen as a suitable heterogenous en-
trainer for the separation of the azeotropic mixture TBA-
water by heteroazeotropic batch distillation. The feasibility
of the heteroazeotropic batch distillation via simulation and
by experiment in a packing column with a special condenser
was confirmed. From the result we can conclude that the
entrainer quantity and the full reflux time significantly
affected the product quality. If too much entrainer is in-
cluded the recovery of main product will decrease. On the
other hand, if there is insufficient entainer the product purity
will not achieve the level required. The distillation process
simulation is an effective instrument for designing heteroge-
neous batch distillations.
______________________
118 http://www.cet-journal.com © 2006 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim
Acknowledgements
The authors thank the National Natural Science Founda-
tion of China (Project No. 20176037) for partial financial
support of this study. Lu Wenhua, Wang Yanfei, Luan Lixia,
and Ren Yankui assisted in the experimental work.
Received: July 22, 2005 [CET 0245]
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