Chemical Engineering & Processing: Process Intensification 130 (2018) 101–109

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Chemical Engineering & Processing: Process Intensification

journal homepage: www.elsevier.com/locate/cep

Energy-saving performance of reactive distillation process for TAME T

synthesis through multiple steady state conditions
⁎ ⁎⁎
Takehiro Yamakia, , Keigo Matsudab,c, , Duangkamol Na-Ranongd, Hideyuki Matsumotoc
a
Research Institute for Chemical Process Technology, National Institute of Advanced Industrial Science and Technology (AIST), AIST Center 5, 1-1-1 Higashi, Tsukuba-shi,
Ibaraki, 305-8565, Japan
b
Department of Chemistry and Chemical Engineering, Graduate School of Science and Engineering, Yamagata University, 4-3-16 Jonan, Yonezawa-shi, Yamagata, 992-
8510, Japan
c
Renewable Energy Center, National Institute of Advanced Industrial Science and Technology (AIST), 2-2-9, Machiikedai, Koriyama, Fukushima, 963-0298, Japan
d
Department of Chemical Engineering, Faculty of Engineering, King Mongkut’s Institute of Technology Ladkrabang, Chalongkrung Road, Bangkok, 10520, Thailand

A R T I C LE I N FO A B S T R A C T

Keywords: We have previously reported the existence of steady-state solutions where reaction conversion is improved
Reactive distillation process within multiple steady states, which appear in the reactive distillation column for tert-amyl methyl ether (TAME)
Multiple steady states synthesis. In the present study, we examined the energy-saving performance of a reactive distillation process that
Reaction conversion comprises a reactive distillation column and two recovery distillation columns for multiple steady state condi-
Process intensification
tions using steady-state process simulation. Bifurcation analysis revealed that the multiple steady state did not
TAME synthesis
exist under a reflux ratio of 1, but existed under reflux ratios of 2, 3, and 4. The reboiler duty required to obtain
high-purity TAME increased with increase in reflux ratio. The evaluation of energy consumption revealed that
the reboiler duties of the second recovery column at the steady-state solutions in the multiple steady state were
lower than that at the steady-state solution of reflux ratio 1. Due to the high reaction conversion and reduction of
the reboiler duty in the second recovery column, the energy inputs per mole of TAME product at steady-state
solutions of the multiple steady state with reflux ratios of 2, 3, and 4 reduced by 17, 12, and 6%, respectively,
compared to that for reflux ratio 1.

1. Introduction
Development of high-efficiency reaction and separation processes is
necessary for the chemical industry to reduce greenhouse gas emissions.
To resolve this problem, process intensification as a methodology has
been proposed. Stankiewicz and Moulijn reviewed equipment and
methods that are elements of process intensification and adopted re-
active distillation as one of the methods [1].
Reactive distillation is one of the reactive separation technologies.
In the case of heterogeneous catalytic reaction, the distillation column
is partly filled with a catalyst. When a mixture of reactants is supplied
to the reactive distillation column, chemical reactions occur in the re-
active section filled with the catalyst. The product is removed from the
reactive section by distillation and concentrated in a rectifying or
stripping section. Since reaction and separation can be simultaneously
carried out in reactive distillation, it has advantages such as energy and
capital saving, compact device, increased reactant conversion, and high
selectivity. The applicability of reactive distillation to reactions such as
methyl acetate synthesis [2–4], methyl tert-butyl ether synthesis [5–8],
ethylene glycol synthesis [9,10], silane and chlorosilane production
[11], and hydrodesulfurization [12] has been investigated.
The synthesis of tert-amyl methyl ether (TAME) is one of the reac-
tions utilizing reactive distillation [13]. TAME is synthesized from
methanol (MeOH), 2-methyl-1-butene (2M1B), and 2-methyl-2-butene
(2M2B). The mixture of reactants is fed to a reactive distillation
column, and TAME is synthesized in the reactive section that is filled
with a catalyst. TAME is separated at the stripping section and re-
covered from the bottom-out of the reactive distillation column. The
design of reactive distillation is more complicated than that of a unit
operation process because it is necessary to consider the interaction of
chemical reaction and distillation separation. Subawalla and Fair [14]
provided guidelines on the design of reactive distillation column and

⁎
Corresponding author at: Research Institute for Chemical Process Technology, National Institute of Advanced Indstrial Science and Technology (AIST), AIST Center 5, 1-1-1 Higashi,
Tsukuba-shi, Ibaraki, 305-8565, Japan.
⁎⁎
Corresponding author at: Department of Chemistry and Chemical Engineering, Graduate School of Science and Engineering, Yamagata University, 4-3-16 Jonan, Yonezawa-shi,
Yamagata, 992-8510, Japan.
E-mail addresses: takehiro-yamaki@aist.go.jp (T. Yamaki), matsuda@yamagata-u.ac.jp (K. Matsuda).

https://doi.org/10.1016/j.cep.2018.05.020
Received 12 March 2018; Received in revised form 8 May 2018; Accepted 30 May 2018
Available online 06 June 2018
0255-2701/ © 2018 Elsevier B.V. All rights reserved.
T. Yamaki et al. Chemical Engineering & Processing: Process Intensification 130 (2018) 101–109

reported simulation results for TAME synthesis designed according to 2. Simulation model
the guidelines. Al-Arfaj and Luyben proposed a reactive distillation
process for TAME synthesis using a reactive distillation column and two 2.1. Reaction kinetics and physical properties
recovery distillation columns [15]. In the first recovery column, MeOH
is recovered from the bottom-out and recycled to the reactive distilla- TAME is produced by the reaction of 2M1B and 2M2B with MeOH.
tion column and the pre-reactor. The distillate flow is fed to the second The following liquid-phase reversible reactions are considered.
recovery column, where 2M1B, 2M2B, and inert components are ob-
2M1B + MeOH ⇄ TAME (1)
tained from the bottom-out. The distillate flow of the second recovery
column including MeOH is returned to the first recovery column. By 2M2B + MeOH ⇄ TAME (2)
recovering and recycling MeOH, reactant loss can be reduced.
In addition, due to the interaction between chemical reaction and 2M1B ⇄ 2M2B (3)
distillation separation, nonlinear phenomena, especially multiple Reaction kinetic models have been proposed [15,19], and the ex-
steady states, occur. A multiple steady state is a state where there are istence of multiple steady state was confirmed. This study employed the
multiple outputs (or inputs) for one input (or output). Mohl et al. ex- reaction kinetics model using the simple power-law model reported by
perimentally confirmed the existence of multiple steady states in a Al-Arfaj and Luyben [15]. They applied the parameters for the reaction
pilot-scale reactive distillation column for TAME synthesis [16]. Rap- kinetics determined based on the results of the heterogeneous reaction
mund et al. [17] and Mohl et al. [18] developed simulation models for system. We have confirmed the existence of multiple steady state from
the reactive distillation column in order to reproduce experimental simulation by applying the reaction kinetic model [21]. The kinetics
results. They confirmed the existence of multiple steady states from the parameters for the forward and reverse reactions are also given by Al-
results of process simulation. Further, Baur et al. reported that the Arfaj and Luyben [15]. To predict the vapor–liquid equilibrium of the
conditions for the appearance of multiple steady states can be clarified mixture containing the reactants, TAME, and inert components, the
by bifurcation analysis [19]. Wilson-RK model was used [16]. The parameter for the Wilson-RK
We analyzed the reaction conversion of reactive distillation column model was adopted in a database of Aspen Plus (V8.0).
for TAME synthesis in multiple steady states. A dynamic simulator was
used to examine the dynamic characteristics of the multiple steady
states, and an operation method in the multiple steady state was pro- 2.2. Reactive distillation column
posed [20]. In addition, we evaluated the effects of operation within the
multiple steady state on the reaction conversion [21]. In a multiple Fig. 1 is a schematic diagram of the reactive distillation column
steady state composed of three branches, upper, middle, and lower, it examined in the present study. The reactive distillation column for
was found that reaction conversion at the upper branch was the highest TAME synthesis consists of rectifying, reactive, and stripping sections. A
and increased with the reflux ratio. However, a high reflux ratio re- mixture of 2M1B, 2M2B, MeOH, and inert components were fed to the
quires a large reboiler duty. Although reaction conversion improves reactive distillation column, and the TAME synthesized in the reactive
under the multiple steady state at a high reflux ratio, the energy con- section was separated at the stripping section and recovered from the
sumption of TAME production in the reactive distillation column also bottom-out stream. On the other hand, unreacted and inert components
increases. were obtained from the distillate stream. Here, generally the reactive
In a previous study, we focused on the reactive distillation column; distillation column is equipped with a pre-reactor to prevent catalyst
however, as reported by Al-Arfaj and Luyben, recovery distillation degradation [14]. We confirmed the existence of multiple steady states
columns for recovering and recycling unreacted materials were pro- from the simulation of a reactive distillation column equipped with a
vided after the reactive distillation column [15]. Improvement of re- pre-reactor. The pre-reactor affects the appearance region of the
action conversion in the reactive distillation column leads to not only
an increase in the amount of TAME product, but also a reduction in the
amounts of unreacted components. The energy consumption of the re-
covery distillation columns may be decreased by reducing the amounts
of unreacted components. If the decrease in energy consumptions of the
recovery distillation columns is larger than the increase in energy
consumption of the reactive distillation column when operated in the
multiple steady state, the reactive distillation process comprising the
reactive distillation column and recovery columns becomes energy-
saving.
In this study, we investigated the energy-saving performance of
reactive distillation process for TAME synthesis through multiple steady
state conditions. In the reactive distillation process, a reactive distilla-
tion column and two recovery distillation columns were used. First, a
model of the reactive distillation column was developed, and the
multiple steady states were determined by bifurcation analysis. The
reaction conversion at the steady-state solutions in the multiple steady
state was compared. Then, a simulation model of the reactive distilla-
tion process for the steady-state solution in multiple steady state was
developed, and the energy consumptions of the recovery columns were
quantitatively evaluated. The effect of operating condition of the re-
active distillation column on the energy consumption of the recovery
column is clarified, and the contribution to the reduction of energy
consumption of the reactive distillation process by improving the re-
action conversion is discussed.

Fig. 1. Schematic diagram of a reactive distillation column for TAME synthesis.

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Table 1 distillation column with a mixture of 2M1B, 2M2B, and inert compo-
Input parameters for simulation model of the reactive distillation column. nents. By adjusting the flow rate of MeOH in the mixture, the flow rate
Design conditions of MeOH fed to the reactive distillation column was kept constant at
141.6 kmol/h, as shown in Fig. 1. It should be noted that the flow rates
Total stage number 33 stages of the reactants 2M1B and 2M2B were unchanged. Thus, the total
Rectifying section 5 stages
amount of reactants and inert components fed to the reactive distilla-
Reactive section 14 stages
Stripping section 14 stages
tion process was constant. The distillate flow from the first recovery
Feed location 15th stage column was fed to the second recovery column, from which 2M1B,
Amount of catalyst 1100 kg 2M2B, and an inert component were obtained from the bottom-out
Bulk density of catalyst 900 kg/m3 stream. On the other hand, the distillate flow from the second recovery
Reactive stage holdup 1.22 m3
column was returned to the first recovery column.
Operating conditions
Pressure of the top 253 kPa The number of stages of the two recovery distillation columns is
Pressure drop of stage 1 kPa eight [15]. In the first recovery column, 99.9 mol% MeOH was re-
Reflux ratio 1–4 – covered from the bottom-out stream, while in the second recovery
Reboiler duty Variable MW
column, a mixture containing less than 0.01 mol% of MeOH was re-
covered from the bottom-out stream. To satisfy these conditions, the
feed locations for the two recovery distillation columns were adjusted
multiple steady states, but has little influence on the presence or ab-
to the 6th stage, and the operating variables were also adjusted. A
sence of the multiple steady state. Thus, in this study, a simulation
model of the two recovery distillation columns was developed using
model of reactive distillation column was developed without con-
RadFrac model in Aspen Plus.
sidering the pre-reactor in order to clarify the effect of reaction con-
version in the reactive distillation column on the energy consumptions
of the recovery columns. 3. Simulation results and discussion
Table 1 shows the design and operating conditions of the reactive
distillation column [21]. A mixture of 2M1B, 2M2B, MeOH, and inert 3.1. Multiple steady state in reactive distillation column
components was fed to the 15th stage of the reactive section. As men-
tioned above, the mixture did not contain TAME. TAME was synthe- In the reactive distillation column for TAME synthesis presented in
sized in the reactive section and recovered from the bottom-out stream. this study, multiple steady states can yield multiple TAME product
The TAME purity and bottom-out flow rate were controlled by the purities for a single reboiler duty [21]. Fig. 3 shows the result of bi-
operating variables, reflux ratio, and reboiler duty. A model of the re- furcation analysis for the mole fraction of TAME in the bottom-out
active distillation column was developed using RadFrac model in Aspen stream using reboiler duty as a bifurcation parameter. Here, we per-
Plus. formed bifurcation analysis by varying the reflux ratio, which is one of
the operating variables, as 1, 2, 3, and 4. At a reflux ratio of 1, the
TAME purity in the bottom-out stream increased with increase in re-
2.3. Recovery distillation columns boiler duty and no multiple steady state occurred. On the other hand,
multiple steady states were present at reflux ratios of 2, 3, and 4. The
Fig. 2 shows a reactive distillation process consisting of a reactive region where the multiple steady states existed was different for each
distillation column and two recovery distillation columns. The distillate reflux ratio. At reflux ratios of 2, 3, and 4, multiple steady states oc-
flow from the reactive distillation column was fed to the first recovery curred in the reboiler duty between 12.25 and 12.12 MW, 16.73 and
column, from which MeOH was obtained from the bottom-out stream 16.25 MW, and 21.27 and 20.49 MW, respectively. The reboiler duty
and returned to the reactive distillation column. The MeOH obtained required to obtain high-purity TAME increased under a high reflux
from the bottom-out of the first recovery column was fed to the reactive ratio.

Fig. 2. Schematic diagram of a reactive distillation column including two recovery columns.

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Fig. 3. Bifurcation diagrams for mole fraction of TAME in the bottom-out flow as a function of reflux ratio and reboiler duty.

3.2. Reaction conversion in multiple steady state Table 3

Distillate flow rate and its composition for steady states 1, 2, 3, and 4.
In this study, four steady-state solutions were selected and their Steady state
reaction conversions in the multiple steady state were compared, as
shown in Fig. 3. At a reflux ratio of 1, the TAME product was achieved 1 2 3 4
with a reboiler duty of 8.25 MW. At reflux ratios of 2, 3, and 4, three
Flow rate kmol/h 690 657 649 646
steady-state solutions of the upper branch, which were obtained at in- Mole fraction [-]
termediate values of reboiler duty in the multiple steady state, were MeOH 0.125 0.106 0.101 0.099
selected. The reboiler duties for reflux ratios of 2, 3, and 4 were 12.19, 2M1B 0.019 0.020 0.021 0.023
16.49, and 20.88 MW, respectively. Table 2 summarizes the simulation 2M2B 0.154 0.137 0.131 0.127
Inert 0.702 0.737 0.747 0.751
results at four steady-state solutions. Here, the reaction conversion
(εMeOH) was calculated using the MeOH flow rate in the feed (F), dis-
tillate (D), and bottom (B):
The MeOH reactant conversions of the steady-state solutions ob-
(F − (DMeOH + BMeOH )) tained at different reflux ratios were compared. The MeOH reactant
εMeOH = MeOH
FMeOH (4) conversions of steady states 1, 2, 3, and 4 were 38.7, 50.7, 53.6, and
54.6%, respectively. Table 3 shows the distillate flow rates and mole
fractions of components at steady states 1, 2, 3, and 4. The distillate
Table 2 flow rate of steady state 4 was the lowest. Although the mole fraction of
Simulation results at steady-state solutions for each reflux ratio. 2M1B in the distillate flow rate for each steady-state solution was al-
Steady state Input variables Output variables most the same, the mole fractions of MeOH and 2M2B decreased while
that of the inert component increased in the following order of steady
RR QR xB,TAME D B εMeOH states: 1, 2, 3, and 4. This is because the amounts of reactants decreased
[-] [MW] [-] [kmol/h] [kmol/h] [%]
under the conditions of high reaction conversion. A high reaction
1 1.00 8.25 1.000 690 54.68 38.7 conversion implies that the reactants were consumed, and conse-
2 2.00 12.19 1.000 657 71.64 50.7 quently, the distillate flow rate decreased. Since the recovered amount
3 3.00 16.49 1.000 649 75.65 53.6 of MeOH decreases, there is a possibility that the energy consumption
4 4.00 20.88 1.000 646 77.11 54.6
of the two recovery distillation columns can be reduced.
RR: reflux ratio; QR: reboiler duty; xB,TAME: liquid composition of TAME in
bottom-out stream; D: distillate flow rate; B: bottom flow rate; εMeOH: MeOH
reaction conversion.

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Fig. 4. Simulation result of reactive distillation process for steady state 1.

3.3. Energy consumption of recovery distillation columns
In order to evaluate the effect of reaction conversion on the energy
consumptions of the two recovery distillation columns, we simulated
the reactive distillation process comprising a reactive distillation
column and two recovery distillation columns. Based on the calculation
results shown in Table 2, calculations were carried out for steady states
1, 2, 3, and 4. Here, the result of steady state 1 was adopted as a re-
ference.
Fig. 4 shows the simulation result for steady state 1 as a reference.
The mole fraction of MeOH in the bottom-out stream of the first re-
covery column is 0.999. The recovered MeOH was returned to the re-
active distillation column. In the second recovery column, separation
was carried out until the mole fraction of MeOH in the bottom-out
stream reached 0.0001 or less. The energy consumptions of the first and
second recovery columns were 11.11 and 13.11 MW, respectively. The
total reboiler duty of the reactive distillation column and the two re-
covery columns was 32.47 MW.
Fig. 5 shows the simulation result for steady state 2. The energy
consumptions of the first and second recovery columns were 11.13 and
11.78 MW, respectively. The energy consumption of the first recovery
column at steady state 2 was almost the same as that of the first re-
covery column at steady state 1. As the reflux ratio of the first recovery
column at steady state 1 is small, there is no duty of separation. Thus,
even if the amount of MeOH fed to the first recovery column decreases
at steady state 2, the effect on energy consumption would be small. On

Fig. 5. Simulation result of reactive distillation process for steady state 2.

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Fig. 6. Reboiler duty for reactive distillation process for steady states 1, 2, 3,
and 4.
Fig. 7. Energy consumption required to produce 1 mol of TAME using reactive
distillation process.
the other hand, the energy consumption of the second recovery column
at steady state 2 decreased as compared with that at steady state 1. The
bottom-out flow rate of the second recovery column at steady state 2 is
smaller than that of the second recovery column at steady state 1. This
is because the reaction conversion in the reactive distillation column
improved at steady state 2, and the amount of unreacted 2M2B reduced.
The throughput of 2M2B at the second recovery column reduced, and
consequently, the energy consumption of the second recovery column
also reduced.
We evaluated the energy consumption of the reactive distillation
process for steady states 3 and 4 as well. Fig. 6 summarizes the total
energy consumption of the reactive distillation process at steady states
1, 2, 3, and 4. Details of the simulation results of the reactive distillation
process at steady states 1, 2, 3, and 4 are shown in Appendix Figs.
A1–A4. In the range of this study, the reboiler duty of the first recovery
column was the highest at steady state 3 (11.21 MW) and the lowest at
steady state 4 (10.95 MW). Note that the difference was as small as
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Chemical Engineering & Processing: Process Intensification 130 (2018) 101–109
0.26 MW. The reboiler duty of the second recovery column was the
highest at steady state 1 (13.11 MW). It was found that the reboiler duty
of the second recovery column can be reduced by improving the reac-
tion conversion in the reactive distillation column. Although the energy
consumptions of the two recovery distillation columns at steady states
2, 3, and 4 reduced compared to those of the two recovery distillation
columns at steady state 1, the reboiler duties of the reactive distillation
column at steady states 2, 3, and 4 were higher than that of the reactive
distillation column at steady state 1. Therefore, the total energy con-
sumption of the reactive distillation process was the lowest at steady
state 1.
3.4. Energy consumption for TAME production using reactive distillation
process
From the above study, it was found that the total energy con-
sumption of the reactive distillation process was the lowest at steady
state 1. However, since the amount of recovered TAME differs at each
steady-state solution as shown in Table 2, the process performance
cannot be evaluated by comparing the total energy consumption of the
reactive distillation process. Thus, it is necessary to discuss the energy
input per mole of TAME product.
Fig. 7 shows the energy inputs per mole of TAME product at steady
states 1, 2, 3, and 4. Here, the energy input per mole of TAME product
was calculated from the bottom-out flow rate in the reactive distillation
column and the total reboiler duty of the reactive distillation process
comprising the reactive distillation column and the two recovery dis-
tillation columns. At steady state 1, an input energy of 2137.7 kJ/mol
was required. The energy inputs per mole of TAME product at steady
states 2, 3, and 4 in the multiple steady state were lower than the en-
ergy input per mole of TAME product at steady state 1. Particularly, an
input energy of 1763.8 kJ/mol was required at steady state 2. There is a
reduction of 17.5% in input energy at steady state 2 compared to that at
steady state 1. The energy inputs per mole of TAME product at steady
states 3 and 4 reduced by 12% and 6%, respectively, compared to that
at steady state 1. When the reactive distillation column was operated
under the conditions of high reaction conversion, the reboiler duty of
the reactive distillation column increased; however, the high reaction
conversion leads to an increase in the amount of synthesized TAME and
decrease the energy consumption of the second recovery column. In the
range of this study, we found that the energy inputs per mole of TAME
product at steady states 2, 3, and 4 in the multiple steady state were
lower than that of TAME product at steady state 1 without the multiple
steady state.
4. Conclusions
In this study, the energy consumption of a reactive distillation
process that comprises a reactive distillation column and two recovery
distillation columns was evaluated for TAME synthesis for multiple
steady state conditions. A simulation model of the reactive distillation
column was developed, and the conditions for the appearance of mul-
tiple steady states were examined by bifurcation analysis. The multiple
steady state was not present at the reflux ratio of 1 but existed at the
reflux ratios of 2, 3, and 4. The region where the multiple steady state
existed was different for each reflux ratio. The reboiler duty required to
obtain high-purity TAME increased with increase in reflux ratio.
Further, we evaluated the energy-saving performance of the reactive
distillation process for multiple steady state conditions. This study
compared the energy consumptions at four steady-state solutions from
T. Yamaki et al. Chemical Engineering & Processing: Process Intensification 130 (2018) 101–109

the results of each reflux ratio. The reboiler duties of the first recovery
column at the four steady-state solutions were almost the same.
However, the energy consumptions of the second recovery column at
steady states 2, 3, and 4 were lower than that of the second recovery
column at steady state 1. Due to the high reaction conversion and re-
duction of the reboiler duty in the second recovery column, the energy
inputs per mole of TAME product at steady state solutions 2, 3, and 4 in
the multiple steady state were reduced by 17, 12, and 6%, respectively,
compared to that of steady state 1. The results of this study indicate that
energy saving of the reactive distillation process is possible by changing
the operating conditions within the multiple steady state conditions.
Declarations of interest
None.

Appendix A. The following are the simulation results of the reactive distillation process of steady states 1, 2, 3, and 4

Fig. A1. Simulation result for steady state 1.

Fig. A2. Simulation result for steady state 2.

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Fig. A3. Simulation result for steady state 3.
Fig. A4. Simulation result for steady state 4.
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