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College of Chemistry and Chemical Engineering, Ocean University of China, Qingdao, 266100, 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.
2014 American Chemical Society 6056 dx.doi.org/10.1021/ie403906z | Ind. Eng. Chem. Res. 2014, 53, 60566064
Industrial & Engineering Chemistry Research Article
First, rapid separation of EO from glycols and improved overall C2H4O (EO) + C4 H10O3 (DEG) C6H14O4 (TEG)
selectivity can be expected because of the large volatility (3)
dierence between EO and EG. Second, the heat of reaction
2.2. Ethoxylation Reaction. Ethoxylation is the addition of
can be directly absorbed into the heat required for separation,
EO to compounds with active hydrogen atoms (alcohols,
achieving a natural heat integration that might reduce operating
glycols, acids, esters, amines, amides, alkylphenols, polyols),
costs. In their article, they conducted the synthesis and design
which is usually catalyzed by acids and bases and mainly
of an RD column in terms of a mixed-integer nonlinear
produces nonionic surfactants with numerous practical
programming (MINLP) formulation. Okasinski and Doherty
applications.27 As shown in eqs 4 and 5, ethanol reacts with
addressed the synthesis and design of an RD column for EG
EO in a manner similar to the hydration of EO. The products
production and presented useful insights into the process
are a series of short-chain polymers containing ethylene glycol
development.23 However, we should point out that nearly all of
monoethyl ether (EGME), diethylene glycol monoethyl ether
the publications regarding EG production by RD emphasized
(DEGME), and so on
the use of distillation to enhance (or intensify) reaction (i.e., to
improve selectivity and utilize heat of reaction). To our C2H4O (EO) + C2H6O (EtOH) C4 H10O2 (EGME)
knowledge, there have not yet been any reports applying the (4)
hydration of EO in an RD column to break azeotropic
limitations to separate azeotropic mixtures containing water. C2H4O (EO) + C4 H10O2 (EGME)
This work proposes a novel application of RD technology for
C6H14O3 (DEGME) (5)
the removal of water from near-azeotropic ethanolwater
mixtures based on the hydration of EO. By contrast to the However, according to our knowledge, no study has focused
process employing IB as the reactive entrainer suggested by on the kinetics of the ethoxylation of ethanol. Hence, we
Dirk-Faitakis and Chuang,20 the chemical reactions presented carried out experiments in a stainless steel 2 L batch reactor at
in this work are irreversible and not equilibrium-limited. Thus, Liaoning Oxiranchem, Inc. (Liaoyang, China), and obtained the
complete conversions of EO and water together with relevant kinetic data. Detailed information regarding the
anhydrous ethanol are expected theoretically. The main apparatus and experimental procedure were described
objectives of this work were to investigate the feasibility of previously.28 From the kinetics experiments, we found that, in
the proposed approach and to identify suitable parameters for the absence of catalysts, the ethoxylation rate of ethanol is
preliminary process design by means of computer simulations. much less than the hydration rate of EO. However, because a
high concentration of ethanol is maintained in the RD column,
2. CHEMICAL REACTION KINETICS the formation of EGME and DEGME cannot be neglected.
2.1. Hydration Reaction. The reaction kinetics of Therefore, the kinetics of the ethoxylation of ethanol is also
hydration of EO has been studied for many years.2426 One considered in this study, as listed in Table 1. Based on the
of the most recent kinetic models of EO hydration was mechanism of ethoxylation, the two reactions have approx-
developed by Altiokka and Akyalcin,26 who studied the kinetics imately the same rate constant and activation energy.2931 It is
experimentally using a pressurized batch reactor. In the cited pointed out that all of the reactions (reactions 15) are
work, the authors provided detailed kinetic data with and irreversible and highly exothermic (approximately 100 kJ/mol
without a catalyst. Because the noncatalytic hydration of EO for of EO reacted).
the production of EG is a well-known process that is widely
used in industrial practice (in most cases within a tubular 3. THERMODYNAMIC CHARACTERISTICS
reactor),26 it was used in this work for the removal of water. The Aspen Plus software package32 was employed for the
The corresponding uncatalyzed reaction kinetic equations are calculation of the thermodynamic properties and phase
listed in Table 1, as provided by Altiokka and Akyalcin.26 behavior of the studied systems. As was done by Dirk-Faitakis
and Chuang,20 the UNIQUAC (universal quasichemical)
Table 1. Reaction Kinetics activity coecient model for the liquid phase and the
RedlichKwong equation of state for the vapor phase were
reaction rate [mol/(Lmin)]
used for phase equilibrium calculations, where UNIQUAC
1 8.22 105 exp(8220/T)CEOCH2O binary interaction parameters were taken from Aspens database
2 5.78 106 exp(8700/T)CEOCEG or estimated by Aspen Plus using the UNIFAC (universal
3 9.44 106 exp(8900/T)CEOCDEG functional activity coecient) model. The thermodynamic
4 7.60 104 exp(9340/T)CEOCEtOH parameters were obtained directly from the Aspen Plus
5 7.60 104 exp(9340/T)CEOCEGME 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,
Future work will attempt to extend this study to catalytical EO 283.6 K; EtOH, 351.4 K; H2O, 373.2 K; EGME, 408.2 K; EG,
hydration processes. As shown in eqs 13, EG is formed from 470.5 K; DEGME, 475.1 K; DEG, 518.0 K; TEG, 561.5 K.
the hydration of EO and can continue to react with EO to form Note that there are obvious dierences in the boiling points
DEG and TEG. In this work, EG is the desired product; hence, among pure components and that the products are much less
the RD process should be designed to obtain the highest volatile than the reactants, which suggests that the separation of
possible selectivity to EG. ethanol from products using an RD column should be
applicable. Moreover, it was found that, in addition to the
C2H4O (EO) + H 2O C2H6O2 (EG) (1) ethanolwater azeotrope, the reactant water and product
EGME can also form a homogeneous azeotrope. Table 2 lists
C2H4O (EO) + C2H6O2 (EG) C4 H10O3 (DEG) (2) the boiling points and azeotropic compositions of the existing
6057 dx.doi.org/10.1021/ie403906z | Ind. Eng. Chem. Res. 2014, 53, 60566064
Industrial & Engineering Chemistry Research Article
Table 3. Parameter Values for the Base Case and the Final indicating that reactions 25 are favored at high temperatures.
Design (This is because the rates of reactions 25 are more sensitive to
the temperature than that rate of reaction 1, as can be seen
parameter base case nal design
from the higher activation energies.) (3) The recovery of
column pressure (MPa) 0.6 0.6 ethanol shows a trend similar to that of water conversion (the
feed rate of ethanolwater mixture (kmol/h) 100 100 slight drop after 0.6 MPa can also be attributed to the increased
molar composition of ethanolwater feed 80:20 80:20 rates of side reactions). (4) The selectivity of EG displays a
number of stagesa 22 22 continuing decrease, because the operating pressure aects the
feed stage location (above stage) 18 17 concentration of EO in the liquid phase in the reactive zone,
liquid holdup (m3) 0.5 1.1 which varies the reaction rates as well as the product selectivity.
feed rate of EO (kmol/h) 25 30 With a lower operating pressure, the concentration of EO in
molar feed ratio of EO to water 1.25:1 1.5:1 the liquid phase is maintained at a lower level, which benets
distillate rate (kmol/h) 78 80.5 the suppression of subsequent side reactions. Conversely, a
reux ratio 5 7 higher operating pressure means a higher EO concentration in
a
Including the condenser (stage 1) and reboiler (stage 22). the liquid phase, which results in increased rates of side
reactions. Thus, the operating pressure should not be too high.
balances). Taking into account the complexity of the To ensure high conversions of water and EO and a high EG
integration of reaction and separation in the same column, a selectivity, 0.6 MPa was selected as the optimum column
sensitivity analysis was conducted primarily to analyze how the pressure.
key parameters impact the column performance. In each 5.2. Eects of EO/Water Molar Feed Ratio. The feed
analysis of a certain parameter, other variables remained ratio of EO to water, an important operating parameter for the
constant at the values listed in Table 3. studied problem, aects both the reactions and separation. To
5.1. Eects of Pressure. Column pressure is one of the achieve a nearly complete conversion of water, the molar feed
most important design parameters for RD. It not only aects ratio of EO to water should be at least greater than 1, according
the relative volatilities of the components and the phase to their stoichiometric coecients in the reactions. Within this
equilibrium, but also has signicant impacts on the chemical range, a low EO/water feed ratio favors a high EG selectivity
kinetics. The column pressure sets the temperature range because of the low concentration of EO, whereas a high ratio is
within the column, which consequently determines the reaction benecial to a high water conversion and a low EG selectivity.
temperature (because chemical reactions take place in the Figure 4 illustrates this analysis well. As the EO/water molar
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 13. Proles of vapor and liquid molar ow rates along the RD
column.
Figure 11. Composition proles in the liquid phase along the RD utilization of reaction heat in the RD column helps to reduce
column. the heat duty of the reboiler.
The relative volatility of ethanol with respect to water along
The temperature prole is mainly determined by the the column is shown in Figure 14. An interesting phenomenon
composition of the components, as demonstrated in Figure
12. The temperature changes little above stage 17, because of
Figure 14. Prole of the relative volatility of EtOH with respect to that
of H2O along the RD column.
Figure 12. Temperature prole along the RD column.
is observed that the azeotropic limitation is actually stepped
the insignicant change in component composition. However, past twice: once at stage 14 and again at stage 19. This can be
below stage 17, the temperature increases dramatically stage by explained by the eects of the combination of reaction and
stage, because of the enrichment of heavy components under distillation. Initially, the volatility of ethanol is higher than that
the eects of separation. of water at the feed stage, because the concentration of ethanol
Figure 13 shows the proles of the vapor and liquid molar is less than the azeotropic composition. However, the
ow rates along the column. It should be noticed that, between concentration of water decreases dramatically after entering
stages 17 and 21 (below the feed location), the molar ow rate the column as a result of the hydration reaction, which changes
of vapor is quite close to that of liquid or even higher, which is the molar ratio of ethanol to water to 0.98:0.02, greater than
dierent from the situation in a conventional distillation the azeotropic composition (0.91:0.09) at the specied
column. This can be attributed to the heat eect of the reaction. operating pressure. Thus, the volatilities of ethanol and water
Because all reactions in the system are highly exothermic, the are shifted, and the azeotropic limitation is circumvented at
heat released by reaction vaporizes part of the liquid directly, stages 14 and 19. Between stages 1 and 14, the fact that relative
which leads to the change in ow rate proles of vapor and volatility of ethanol to water is quite close to 1, as indicated in
liquid along the column. As is known, one substantial advantage Figure 14, implies that the direct separation of water from
of an RD column is that the heat of reaction can be utilized in ethanol by distillation is dicult. This again suggests that the
the column, which is well reected in this study. Such direct removal of water from the system is accomplished mainly by
6062 dx.doi.org/10.1021/ie403906z | Ind. Eng. Chem. Res. 2014, 53, 60566064
Industrial & Engineering Chemistry Research
Article
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 NOMENCLATURE
components can further aect the relative volatility of water and Ci = molarity of component i (mol/L)
ethanol. This will be further studied in future work on process P = pressure (MPa)
development. T = reaction temperature (K)
5.8. Energy Considerations. To illustrate the advantages xi = mole fraction of component i
of the proposed process, the energy consumption is compared wi = mass fraction of component i
with other reported processes for purifying ethanol.34 The
Abbreviations
reboiler heat duty in the proposed process is 5.32 MJ per
kilogram of anhydrous ethanol, implying a reduction of 45 CD = catalytic distillation
75% in energy consumption compared with azeotropic DEG = diethylene glycol
distillation (10.0515.49 MJ/kg) and extractive distillation DEGME = diethylene glycol monoethyl ether
(9.2118.84 MJ/kg). In addition, the bottom product, EG = ethylene glycol
containing EG, DEG, TEG, EGME, and DEGME, also EGME = ethylene glycol monoethyl ether
generates great economic benets for its wide usage in the EO = ethylene oxide
ne-chemistry industry, which also shows its outstanding ETBE = ethyl tert-butyl ether
advantage over other separation process. For the present, IB = isobutylene
detailed economic analysis and comparisons are not considered. MINLP = mixed-integer nonlinear programming
RD = reactive distillation
The energy consumption of the RD process proposed by Dirk-
TBA = tert-butyl alcohol
Faitakis and Chuang20 is reported as 0.22 kWh/kg of product
TEG = triethylene glycol
(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
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