Article

pubs.acs.org/IECR

Simulation and Analysis of a Reactive Distillation Column for

Removal of Water from EthanolWater Mixtures
Weizhong An, Zixin Lin,*, Jun Chen, and Jianmin Zhu

College of Chemistry and Chemical Engineering, Ocean University of China, Qingdao, 266100, China

Liaoning Oxiranchem Group, Liaoyang 111003, China

ABSTRACT: A novel approach to removing water from near-azeotropic ethanolwater mixtures is proposed based on the
hydration of ethylene oxide (EO) to produce ethylene glycol (EG) in a reactive distillation (RD) column. Steady-state
simulations using the Aspen Plus software package were carried out to investigate the feasibility of the suggested approach, and a
sensitivity analysis was carried out to obtain the optimal design parameters. The results showed that, using the optimal operating
conditions, a reactive distillation column is capable of circumventing the azeotropic limitation to obtain anhydrous ethanol.
Compared with traditional approaches, the proposed approach is promising because of its great potential for reducing energy
consumption and capital costs.

1. INTRODUCTION Reactive distillation (RD), also known as catalytic distillation

Driven by several world energy crises that have taken place
since the 1973 oil crisis, demand for ethanol continues to be
high, because ethanol is an excellent alternative clean-burning
fuel to conventional hydrocarbon-based fuels such as gasoline.
Because of the existence of a minimum-boiling azeotrope of
ethanol (95.6 wt %) and water (4.4 wt %), special processes
have to be employed to remove the remaining water from the
mixture. Azeotropic distillation and extractive distillation are
two widely used processes, both of which involve the
introduction of a third component into the mixture.1 For
azeotropic distillation, the added component forms new binary
and/or ternary azeotropes in the system to purify ethanol, as
long as the distillation proceeds in a feasible region of the
residue-curve map.2,3 For extractive distillation, the added
component changes the relative volatility of ethanol with
respect to water, to the extent that separation becomes
practicable.47 Technologies of pervaporation and adsorption
are also commercially used. The former represents a new
generation of membrane separation process involving a phase
change to form a gaseous permeate and liquid retentate using a
semipermeable membrane,8 whereas the latter employs
molecular sieves or biomaterials (e.g., corn grits, cassava starch)
to selectively adsorb water.911 Another process for dehydrat-
ing ethanol is supercritical uid extraction, in which carbon
dioxide is employed as the solvent. Liquid CO2 is used to
extract the ethanol, and then CO 2 is ashed o by
depressurization to recover anhydrous ethanol.12 However,
regardless of whether they are distillation or nondistillation
technologies, all of the above processes involve either
considerable energy consumption or huge capital investments
because of their complex process congurations. In addition,
for some of these processes, large-scale production of
anhydrous ethanol can hardly be achieved because of their
batchwise operation. Taking into account the characteristics of
the separation process in this study, we considered that the
removal of water from ethanolwater mixtures is well-suited to
be carried out in a reactive distillation column.
(CD) when a catalyst (heterogeneous or homogeneous) is
employed, can be considered as a new unit operation that
couples reaction with distillation.13 Because of its potential for
improved process intensication and successful commercial
applications, reactive/catalytic distillation has attracted increas-
ing interest from both academia and industry.14,15 As suggested
by Terrill and co-workers, one application of RD is the
separation of close-boiling mixtures, where a reactive entrainer
is introduced into the column to react selectively with the
original components.16,17 This theory implies the potential for
similar application to azeotropic mixtures, which was, indeed,
conrmed to be feasible.18,19 Dirk-Faitakis and Chuang
successfully proposed a CD process whereby water in a near-
azeotropic ethanolwater mixture was removed by reaction
with isobutylene (IB) to form tert-butyl alcohol (TBA) and,
meanwhile, a portion of ethanol reacted with IB to form ethyl
tert-butyl ether (ETBE).20 As around 90% of the water could be
removed by reaction, the nal product was a mixture containing
mainly ethanol, TBA, and ETBE that was suitable for use as an
oxygenated fuel additive. However, it is noted that this
approach cannot directly obtain high-purity ethanol, because
the reactions to form both TBA and ETBE are reversible and
equilibrium-limited.
In the eld of RD/CD, a number of articles have already
been published on the synthesis of ethylene glycol (EG) by the
hydration of ethylene oxide (EO), as EG is an important raw
material used in the manufacture of poly(ethylene glycol)s with
dierent molecular weights, as well as other polyester resins,
antifreezes, and solvents. Parkers 1958 patent pointed out that
the chemical reactions are highly exothermic and the reaction
conditions are mild enough to allow EG production by RD.21
Ciric and Gu described two reasons for producing EG by RD:22
Received: November 18, 2013
Revised: February 26, 2014
Accepted: February 28, 2014
Published: February 28, 2014

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Industrial & Engineering Chemistry Research
First, rapid separation of EO from glycols and improved overall
selectivity can be expected because of the large volatility
dierence between EO and EG. Second, the heat of reaction
can be directly absorbed into the heat required for separation,
achieving a natural heat integration that might reduce operating
costs. In their article, they conducted the synthesis and design
of an RD column in terms of a mixed-integer nonlinear
programming (MINLP) formulation. Okasinski and Doherty
addressed the synthesis and design of an RD column for EG
production and presented useful insights into the process
development.23 However, we should point out that nearly all of
the publications regarding EG production by RD emphasized
the use of distillation to enhance (or intensify) reaction (i.e., to
improve selectivity and utilize heat of reaction). To our
knowledge, there have not yet been any reports applying the
hydration of EO in an RD column to break azeotropic
limitations to separate azeotropic mixtures containing water.
This work proposes a novel application of RD technology for
the removal of water from near-azeotropic ethanolwater
mixtures based on the hydration of EO. By contrast to the
process employing IB as the reactive entrainer suggested by
Dirk-Faitakis and Chuang,20 the chemical reactions presented
in this work are irreversible and not equilibrium-limited. Thus,
complete conversions of EO and water together with
anhydrous ethanol are expected theoretically. The main
objectives of this work were to investigate the feasibility of
the proposed approach and to identify suitable parameters for
preliminary process design by means of computer simulations.
2. CHEMICAL REACTION KINETICS
2.1. Hydration Reaction. The reaction kinetics of
hydration of EO has been studied for many years.2426 One
of the most recent kinetic models of EO hydration was
developed by Altiokka and Akyalcin,26 who studied the kinetics
experimentally using a pressurized batch reactor. In the cited
work, the authors provided detailed kinetic data with and
without a catalyst. Because the noncatalytic hydration of EO for
the production of EG is a well-known process that is widely
used in industrial practice (in most cases within a tubular
reactor),26 it was used in this work for the removal of water.
The corresponding uncatalyzed reaction kinetic equations are
listed in Table 1, as provided by Altiokka and Akyalcin.26
Table 1. Reaction Kinetics
reaction rate [mol/(Lmin)]
1 8.22 105 exp(8220/T)CEOCH2O
2 5.78 106 exp(8700/T)CEOCEG
3 9.44 106 exp(8900/T)CEOCDEG
4 7.60 104 exp(9340/T)CEOCEtOH
5 7.60 104 exp(9340/T)CEOCEGME
Future work will attempt to extend this study to catalytical EO
hydration processes. As shown in eqs 13, EG is formed from
the hydration of EO and can continue to react with EO to form
DEG and TEG. In this work, EG is the desired product; hence,
the RD process should be designed to obtain the highest
possible selectivity to EG.
C2H4O (EO) + H 2O C2H6O2 (EG)
C2H4O (EO) + C2H6O2 (EG) C4 H10O3 (DEG)
Article
C2H4O (EO) + C4 H10O3 (DEG) C6H14O4 (TEG)
(3)
2.2. Ethoxylation Reaction. Ethoxylation is the addition of
EO to compounds with active hydrogen atoms (alcohols,
glycols, acids, esters, amines, amides, alkylphenols, polyols),
which is usually catalyzed by acids and bases and mainly
produces nonionic surfactants with numerous practical
applications.27 As shown in eqs 4 and 5, ethanol reacts with
EO in a manner similar to the hydration of EO. The products
are a series of short-chain polymers containing ethylene glycol
monoethyl ether (EGME), diethylene glycol monoethyl ether
(DEGME), and so on
C2H4O (EO) + C2H6O (EtOH) C4 H10O2 (EGME)
(4)
C2H4O (EO) + C4 H10O2 (EGME)
C6H14O3 (DEGME) (5)
However, according to our knowledge, no study has focused
on the kinetics of the ethoxylation of ethanol. Hence, we
carried out experiments in a stainless steel 2 L batch reactor at
Liaoning Oxiranchem, Inc. (Liaoyang, China), and obtained the
relevant kinetic data. Detailed information regarding the
apparatus and experimental procedure were described
previously.28 From the kinetics experiments, we found that, in
the absence of catalysts, the ethoxylation rate of ethanol is
much less than the hydration rate of EO. However, because a
high concentration of ethanol is maintained in the RD column,
the formation of EGME and DEGME cannot be neglected.
Therefore, the kinetics of the ethoxylation of ethanol is also
considered in this study, as listed in Table 1. Based on the
mechanism of ethoxylation, the two reactions have approx-
imately the same rate constant and activation energy.2931 It is
pointed out that all of the reactions (reactions 15) are
irreversible and highly exothermic (approximately 100 kJ/mol
of EO reacted).
3. THERMODYNAMIC CHARACTERISTICS
The Aspen Plus software package32 was employed for the
calculation of the thermodynamic properties and phase
behavior of the studied systems. As was done by Dirk-Faitakis
and Chuang,20 the UNIQUAC (universal quasichemical)
activity coecient model for the liquid phase and the
RedlichKwong equation of state for the vapor phase were
used for phase equilibrium calculations, where UNIQUAC
binary interaction parameters were taken from Aspens database
or estimated by Aspen Plus using the UNIFAC (universal
functional activity coecient) model. The thermodynamic
parameters were obtained directly from the Aspen Plus
database and compared with literature data.33 The boiling
points at atmospheric pressure of the eight components
involved in this study are as follows (from low to high): EO,
283.6 K; EtOH, 351.4 K; H2O, 373.2 K; EGME, 408.2 K; EG,
470.5 K; DEGME, 475.1 K; DEG, 518.0 K; TEG, 561.5 K.
Note that there are obvious dierences in the boiling points
among pure components and that the products are much less
volatile than the reactants, which suggests that the separation of
ethanol from products using an RD column should be
applicable. Moreover, it was found that, in addition to the
(1) ethanolwater azeotrope, the reactant water and product
EGME can also form a homogeneous azeotrope. Table 2 lists
(2) the boiling points and azeotropic compositions of the existing
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Table 2. Azeotropic Data for the System
mixture Taz (K) xaz,1 waz,1 Paz (MPa)
ethanol (1)water (2) 351.3 0.8968 0.9569 0.1013
404.7 0.9146 0.9648 0.6
water (1)EGME (2) 372.7 0.9321 0.7329 0.1013
441.7 0.8869 0.6106 0.6
azeotropes at 0.1013 and 0.6 MPa33 (where 0.6 MPa is the
recommended operating pressure of the RD column, as will be
seen later in this article). However, in fact, the formation of a
waterEGME azeotrope occurs only in theory: It is not
possible in the proposed RD column because the concentration
of water along the column is too low (less than 0.03, as will be
seen later in this article). In other words, the azeotropic
limitation of the waterEGME mixture need not be considered
in the preliminary design and simulation analysis of the
proposed approach.
Figure 1 shows the binary ethanolwater diagram at 0.6 MPa
as calculated with Aspen Plus using the UNIQUAC model,
Figure 1. Binary diagram for the EtOHH2O system at P = 0.6 MPa.
which is divided into two regions by the azeotropic
composition (ethanol molar fraction of 0.9146). In this study,
the composition of the ethanolwater feed is located in region
1, which is xed at a molar ratio of 80:20 (ethanol/water), near
the azeotropic composition. After the feed has entered the
column, the concentration of water decreases sharply to a low
level as a result of its consumption in the hydration of EO.
Once the molar composition of ethanol is greater than 0.9146,
the azeotropic limitation is circumvented. Thus, both reaction
and separation of the reactants and products occur in region 2
simultaneously. Meanwhile, it is noted that, in region 2, water is
more volatile than ethanol (as can be seen later in Figure 14),
which means that water will be distilled together with ethanol
from the top of the RD column. Thus, to obtain absolute
ethanol, a nearly complete conversion of water must be
achieved. The thermodynamic properties and phase behavior
described above provide useful insights into the process design,
as discussed in the next section.
4. RD COLUMN CHARACTERISTICS
Figure 2 shows a schematic of the proposed RD column used in
the simulations. It includes a total condenser and a partial
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Figure 2. Schematic of the RD column.
reboiler. For simplication, the RD column has only one feed
inlet, where the ethanolwater mixture is rst mixed with EO
and then enters the column. Based on the feed location and the
volatility of the EO reactant, the RD column can be divided
into two sections, namely, a reactive zone and a stripping
section, as shown in Figure 2. In the reactive zone, because EO
can occur on each stage because of its high volatility and
because the reactions are homogeneous without catalysts, the
reaction and separation actually proceed simultaneously. In the
stripping section, because of the high volatility of EO, the
concentration of EO in the liquid phase is so low that this
section mainly performs the separation of the products from
the reactants. The overhead product is anhydrous ethanol,
whereas the bottom product is a mixture containing all of the
reaction products.
The key operating parameters of the RD column include the
column pressure, molar EO/water feed ratio, distillate-to-feed
ratio, reux ratio, and holdups, which have signicant eects on
the column performance. When designing the RD column,
both objectives of reaction and separation should be
considered. The objectives of reaction include the conversion
of water and EO and the selectivity of EG, all of which are
preferred to be as high as possible. The objectives of separation
mainly include the separation eciency of ethanol, in other
words, the recovery of ethanol in the overhead product, which
is the ratio of the molar ow rate of ethanol from the top of the
column to the molar ow rate of ethanol in the feed. The
objective of ethanol recovery is greater than 99.0% separation
eciency (the column bottom product should not contain any
ethanol). It is noticed that, to achieve these objectives, water
should be converted almost completely. In addition, energy
consumption is also an important target in this study: Lower
energy consumption indicated by the usage of the reboiler heat
duty is desired. Table 3 lists the operating parameters and the
values for the base case used in the simulation. These
conditions are close to the optimal values, as discussed in the
following sections.
5. RESULTS AND DISCUSSION
Simulation studies were conducted with the steady-state
fractionation model RADFRAC from the process simulator
Aspen Plus, which is based on a rigorous equilibrium stage
model for solving the MESH equations (material balances,
equilibrium relationships, summation equations, and heat
dx.doi.org/10.1021/ie403906z | Ind. Eng. Chem. Res. 2014, 53, 60566064
Industrial & Engineering Chemistry Research
Table 3. Parameter Values for the Base Case and the Final
Design
parameter base case nal design
column pressure (MPa) 0.6
feed rate of ethanolwater mixture (kmol/h) 100
molar composition of ethanolwater feed 80:20
number of stagesa 22
feed stage location (above stage) 18
liquid holdup (m3) 0.5
feed rate of EO (kmol/h) 25
molar feed ratio of EO to water 1.25:1
distillate rate (kmol/h) 78
reux ratio 5 7
a
Including the condenser (stage 1) and reboiler (stage 22).
balances). Taking into account the complexity of the
integration of reaction and separation in the same column, a
sensitivity analysis was conducted primarily to analyze how the
key parameters impact the column performance. In each
analysis of a certain parameter, other variables remained
constant at the values listed in Table 3.
5.1. Eects of Pressure. Column pressure is one of the
most important design parameters for RD. It not only aects
the relative volatilities of the components and the phase
equilibrium, but also has signicant impacts on the chemical
kinetics. The column pressure sets the temperature range
within the column, which consequently determines the reaction
temperature (because chemical reactions take place in the
liquid phase, the reaction temperature is close to the boiling
point of the liquid phase) and then further aects the reaction
rate. A low temperature makes the reaction rate low, which
would cause very large liquid holdups. A high temperature is
benecial to high reaction rates, but this could aect the
selectivities of desired products, given that the rates of side
reactions also increase. A sensitivity analysis was performed to
illustrate the eects of pressure, as shown in Figure 3. It can be
seen that, as the column pressure increases from 0.2 to 1.0
MPa, the following changes occur: (1) The conversion of EO
increases because of the increased reaction rate as the
temperature increases. (2) The conversion of water increases
initially, because the hydration rate increases. However, when
the temperature is too high, the water conversion decreases,
Figure 3. Eects of the column pressure on the water conversion, EO
conversion, EtOH recovery, and EG selectivity of the column.
Article
indicating that reactions 25 are favored at high temperatures.
(This is because the rates of reactions 25 are more sensitive to
the temperature than that rate of reaction 1, as can be seen
from the higher activation energies.) (3) The recovery of
0.6 ethanol shows a trend similar to that of water conversion (the
100 slight drop after 0.6 MPa can also be attributed to the increased
80:20 rates of side reactions). (4) The selectivity of EG displays a
22 continuing decrease, because the operating pressure aects the
17 concentration of EO in the liquid phase in the reactive zone,
1.1 which varies the reaction rates as well as the product selectivity.
30 With a lower operating pressure, the concentration of EO in
1.5:1 the liquid phase is maintained at a lower level, which benets
80.5 the suppression of subsequent side reactions. Conversely, a
higher operating pressure means a higher EO concentration in
the liquid phase, which results in increased rates of side
reactions. Thus, the operating pressure should not be too high.
To ensure high conversions of water and EO and a high EG
selectivity, 0.6 MPa was selected as the optimum column
pressure.
5.2. Eects of EO/Water Molar Feed Ratio. The feed
ratio of EO to water, an important operating parameter for the
studied problem, aects both the reactions and separation. To
achieve a nearly complete conversion of water, the molar feed
ratio of EO to water should be at least greater than 1, according
to their stoichiometric coecients in the reactions. Within this
range, a low EO/water feed ratio favors a high EG selectivity
because of the low concentration of EO, whereas a high ratio is
benecial to a high water conversion and a low EG selectivity.
Figure 4 illustrates this analysis well. As the EO/water molar
Figure 4. Eects of the molar feed ratio of EO to water on the water
conversion, EO conversion, EtOH recovery, and EG selectivity of the
column.
feed ratio increases, the EG selectivity decreases, whereas the
water conversion increases. The recovery of ethanol also
increases, because an increased EO concentration is benecial
to reactions 2 and 3, whose reaction rates are more sensitive to
the EO concentration. With these specied parameters, a nearly
complete conversion of EO can be achieved. A molar ratio of
1.5 is nally suggested to strike a balance between high water
conversion and EG selectivity as well as EO conversion.
5.3. Eects of Distillate-to-Feed Ratio. According to the
simulation results, we found that the ratio of distillation to feed
(ethanolwater mixture) is more critical to separation than to
reaction, especially the separation in the stripping section. The
analysis results are shown in Figure 5, from which one can
make the following conclusions: (1) The distillate-to-feed ratio
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Industrial & Engineering Chemistry Research Article

water conversion and EG selectivity as well as the boiler heat

duty, a reux ratio of 7 is suggested as the optimal condition.
5.5. Eects of Feed Location. The location of the feed
stage has signicant impacts on both separation and reaction,
because it determines not only the number of stages in the
stripping section but also the reaction volume in the reactive
zone of the column. As shown in Figure 6, when the feed

Figure 5. Eects of the distillate-to-feed ratio on the water conversion,

EO conversion, EtOH recovery, and EG selectivity of the column.

(D/F) has little eect on the EO conversion, because EO is a

light component that is mainly concentrated in the reactive
zone and rarely enters the stripping section below the feed
stage. (2) For ethanol, a smaller D/F impairs the eect of
separation, leading to a higher concentration of ethanol in the
bottom product, so that the recovery of ethanol is decreased. Figure 6. Eects of the feed location on the water conversion, EO
Conversely, a higher D/F is benecial to a higher recovery of conversion, EtOH recovery, and EG selectivity of the column.
ethanol. (3) A large D/F decreases the water conversion,
mainly because a portion of water is distilled from the top of location is too close to the top of the column, EO can easily
the column together with ethanol. (4) The trend for EG escape from the top because of its low boiling point, which
selectivity is the same as that for water conversion, because a leads to low conversions of EO and water. At the same time,
high water conversion indicates a high generation rate of EG the separation eect of the reactive zone is impaired. Thus,
and, consequently, a high EG selectivity, and vice versa. Above more EO is brought into the stripping section, where EG can
all, D/F is an important operating parameter. According to the further react with EO to form DEG and TEG. As a result, the
analysis, the recommended value of the distillate-to-feed ratio is selectivity to EG decreases. On the other hand, if the feed
around 0.80 for high conversions of water and EO, as well as a location is too close to the bottom of the column, more water
desired ethanol recovery. and ethanol are withdrawn from the bottom because of the
5.4. Eects of Reux Ratio. In RD columns, the reux weakened separation eect of the stripping section, which also
ratio plays an important role in both reaction and separation. results in low water conversion and ethanol recovery. The EG
Table 4 describes the relationships between the reux ratio and selectivity shows a trend similar to that of water conversion.
The above analysis explains well why there exists an optimal
Table 4. Eects of Reux Ratio feed location with the best water conversion and EG selectivity.
Similarly, the recovery of ethanol initially increases and then
reux water EG selectivity EtOH recovery boiler duty
ratio conversion (%) (%) (%) (MW) decreases, also because of the decreased separation eects of
4 87.98 64.89 95.37 3.01
the two extreme cases. However, the EO conversion always
5 89.73 66.54 95.66 3.77
increases as the feed location moves downward, because of the
6 91.01 67.76 95.87 4.53
increase in its residence time in the column. To guarantee a
7 91.97 68.72 96.01 5.28
complete conversion of EO as well as high water conversion
8 92.71 69.52 96.11 6.03
and EG selectivity, the favored feed location is at stage 17.
9 93.29 70.22 96.16 6.79
5.6. Eects of Liquid Holdups. The holdup is one of the
10 93.73 70.86 96.19 7.54
most critical design parameters for RD processes, which mainly
aects reactions because it refers to the reaction volume. In this
study, the liquid holdup on each tray was assumed to be the
same. Figure 7 illustrates the eects of dierent holdups on
water conversion, ethanol recovery, and reboiler heat duty. In water conversion and other characteristics. As expected, the
all of these scenarios, EO is converted completely. It can be larger the liquid holdup, the larger the EO conversion, because
seen that (1) water conversion increases as the reux ratio is the residence time of EO in the reactive zone increases.
increased, because unreacted reactants are forced to recycle However, a large holdup also favors side reactions, which
back to the column for further reaction; (2) the recovery of reduces the conversion of water as well as the selectivity of EG
ethanol increases with increasing reux ratio because of and the recovery of ethanol. To ensure a high conversion of
strengthened separation eects; and (3) the selectivity to EG EO, a volumetric holdup of 1.1 m3 on each tray is nally
exhibits a trend similar to that of water, because the EG selected as the optimal parameter.
concentration is closely related to the water concentration. In 5.7. Simulation Analysis. Figure 8 shows the nal design
addition, the reux ratio has a greater impact on the heat duty, of the RD column. The optimal operating variables gained from
as indicated in Table 4. To arrive at a compromise between the sensitivity analysis are reported in Table 3. The simulation
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Figure 9 displays the proles of the component generation

rates through the length of the column, illustrating that the

Figure 7. Eects of liquid holdups on the water conversion, EO

conversion, EtOH recovery, and EG selectivity of the column.

Figure 9. Proles of component generation rates along the RD

column.

reactions mainly proceed between stages 11 and 17. It can be

seen that the consumption rates of water and EO reach a
maximum at the feed stage (stage 17) because of the maximum
concentration of reactants. On every other stage, reactions also
occur although with relatively low rates. This suggests that
water is removed mainly by reaction with EO, because it is
dicult to directly separate water from ethanol at near-
azeotropic compositions by normal distillation.
Figure 10 shows the composition proles of water and EO
along the column. The mole fraction of water exhibits a

Figure 8. Schematic of the RD column with simulation results under

optimal operating conditions.

results, shown in Figure 8, conrm the feasibility of the

proposed approach. First, anhydrous ethanol (99.6 wt %) is
obtained from the overhead product. The bottom byproduct is
a mixture of EG, DEG, and TEG, plus a small quantity of
EGME and DEGME, which can be either separated further to
obtain pure components or used directly as a solvent for
nitrocellulose, resins, dyes, or other applications. In this work,
further separation of the bottom mixture was not considered.
Second, high conversions of water and EO are realized
simultaneously, as a result of the combination of reaction and Figure 10. Composition proles of H2O and EO in the liquid phase
separation. (Under the eects of separation, unreacted water in along the RD column.
the stripping section is recycled to the reactive zone for further
reaction.) Third, the heat released by reactions is utilized in the maximum at the feed stage and then decreases sharply as a
process, indicated by the greater heat duty of the condenser result of consumption in the reaction. From stage 5, the mole
compared with that of the reboiler. Finally, because of the low fraction of water increases slightly stage by stage until the top of
concentration of water in the column, the selectivity of EG is the column, as a result of the shifted volatilities of ethanol and
53.5%, not as high as that in the conventional RD process to water after the circumvention of the azeotropic limitation, as
produce EG from EO and water. However, our primary well as reduced reaction rates. In this process, the
objective was the removal of water, and the main point of this concentrations of EO and water throughout the column are
study was to emphasize the enhancement of separation through very low, indicating complete conversions of both components.
reaction. The composition proles of other components are shown in
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Industrial & Engineering Chemistry Research
Figure 11, illustrating that heavy components are enriched at
and near the bottom of the column.
Figure 11. Composition proles in the liquid phase along the RD
column.
The temperature prole is mainly determined by the
composition of the components, as demonstrated in Figure
12. The temperature changes little above stage 17, because of
Figure 12. Temperature prole along the RD column.
the insignicant change in component composition. However,
below stage 17, the temperature increases dramatically stage by
stage, because of the enrichment of heavy components under
the eects of separation.
Figure 13 shows the proles of the vapor and liquid molar
ow rates along the column. It should be noticed that, between
stages 17 and 21 (below the feed location), the molar ow rate
of vapor is quite close to that of liquid or even higher, which is
dierent from the situation in a conventional distillation
column. This can be attributed to the heat eect of the reaction.
Because all reactions in the system are highly exothermic, the
heat released by reaction vaporizes part of the liquid directly,
which leads to the change in ow rate proles of vapor and
liquid along the column. As is known, one substantial advantage
of an RD column is that the heat of reaction can be utilized in
the column, which is well reected in this study. Such direct
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Figure 13. Proles of vapor and liquid molar ow rates along the RD
column.
utilization of reaction heat in the RD column helps to reduce
the heat duty of the reboiler.
The relative volatility of ethanol with respect to water along
the column is shown in Figure 14. An interesting phenomenon
Figure 14. Prole of the relative volatility of EtOH with respect to that
of H2O along the RD column.
is observed that the azeotropic limitation is actually stepped
past twice: once at stage 14 and again at stage 19. This can be
explained by the eects of the combination of reaction and
distillation. Initially, the volatility of ethanol is higher than that
of water at the feed stage, because the concentration of ethanol
is less than the azeotropic composition. However, the
concentration of water decreases dramatically after entering
the column as a result of the hydration reaction, which changes
the molar ratio of ethanol to water to 0.98:0.02, greater than
the azeotropic composition (0.91:0.09) at the specied
operating pressure. Thus, the volatilities of ethanol and water
are shifted, and the azeotropic limitation is circumvented at
stages 14 and 19. Between stages 1 and 14, the fact that relative
volatility of ethanol to water is quite close to 1, as indicated in
Figure 14, implies that the direct separation of water from
ethanol by distillation is dicult. This again suggests that the
removal of water from the system is accomplished mainly by
dx.doi.org/10.1021/ie403906z | Ind. Eng. Chem. Res. 2014, 53, 60566064
Industrial & Engineering Chemistry Research
reaction. Between stages 19 and 22, where the volatility of
ethanol is also lower than that of water, a minimum relative
volatility of ethanol with respect to water exists at stage 22. This
is mainly because the separation eect leads to changes in the
component composition and, consequently, inuences the
activity coecients of ethanol and water. Moreover, as the
products of hydration and ethoxylation reactions are heavy
components with higher boiling points than water, these heavy
components can further aect the relative volatility of water and
ethanol. This will be further studied in future work on process
development.
5.8. Energy Considerations. To illustrate the advantages
of the proposed process, the energy consumption is compared
with other reported processes for purifying ethanol.34 The
reboiler heat duty in the proposed process is 5.32 MJ per
kilogram of anhydrous ethanol, implying a reduction of 45
75% in energy consumption compared with azeotropic
distillation (10.0515.49 MJ/kg) and extractive distillation
(9.2118.84 MJ/kg). In addition, the bottom product,
containing EG, DEG, TEG, EGME, and DEGME, also
generates great economic benets for its wide usage in the
ne-chemistry industry, which also shows its outstanding
advantage over other separation process. For the present,
detailed economic analysis and comparisons are not considered.
The energy consumption of the RD process proposed by Dirk-
Faitakis and Chuang20 is reported as 0.22 kWh/kg of product
(0.80 MJ/kg), which is much less than that of our proposed
approach. However, in their study, the molar ratio of ethanol to
water was 88:12, which is higher than what we used in this
study, and the purity of ethanol in the nal product was only
approximately 50% by weight. Extra energy will be required to
obtain absolute ethanol. Thus, the two processes cannot be
compared directly in a simple way without further detailed
analysis.
6. CONCLUSIONS
This work proposes a novel RD process to remove water from
ethanolwater mixtures at near-azeotropic compositions by
reaction with EO, which was conrmed to be feasible according
to the simulations. As water is consumed in the hydration
reaction, the azeotropic limitation is stepped past, and
dehydrated ethanol is distilled from the top of the column.
Optimal operating conditions, including operating pressure,
reux ratio, and liquid holdups, were obtained based on a
sensitivity analysis, subjected to specied conversions of water
and EO as well as other objectives. A reduction in energy
consumption can be achieved by utilizing the heat of reactions
directly in the distillation column. Compared with other
traditional separation processes removing water from ethanol,
the proposed approach shows its promising applications and
great potential in savings in capital investments and energy
consumption. The main objective of this study was to obtain
condence in the feasibility of the proposed process, which was
accomplished successfully. Future work on experimental studies
is being carried out.
AUTHOR INFORMATION
Corresponding Author
*Tel.: +86-532- 66782903. E-mail: linzixin@ouc.edu.cn.
Notes
The authors declare no competing nancial interest.
6063
Article
ACKNOWLEDGMENTS
This research was nancially supported by the National Natural
Science Foundation of China (21306179) and the State Key
Laboratory of Chemical Engineering of China (No. SKL-ChE-
12B03).
NOMENCLATURE
Ci = molarity of component i (mol/L)
P = pressure (MPa)
T = reaction temperature (K)
xi = mole fraction of component i
wi = mass fraction of component i
Abbreviations
CD = catalytic distillation
DEG = diethylene glycol
DEGME = diethylene glycol monoethyl ether
EG = ethylene glycol
EGME = ethylene glycol monoethyl ether
EO = ethylene oxide
ETBE = ethyl tert-butyl ether
IB = isobutylene
MINLP = mixed-integer nonlinear programming
RD = reactive distillation
TBA = tert-butyl alcohol
TEG = triethylene glycol
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