Chemical Engineering Science 63 (2008) 2119 – 2134

www.elsevier.com/locate/ces

Towards further internal heat integration in design of reactive distillation

columns—Part III: Application to a MTBE reactive distillation column
Kejin Huang a,∗ , San-Jang Wang b , Wenming Ding c
a College of Information Science and Technology, Beijing University of Chemical Technology, Beijing 100029, People’s Republic of China
b Department of Chemical and Material Engineering, Ta Hwa Institute of Technology, Chiunglin, Hsinchu 307, Taiwan
c College of Chemical Engineering, Beijing University of Chemical Technology, Beijing 100029, People’s Republic of China

Received 27 March 2007; received in revised form 31 December 2007; accepted 8 January 2008
Available online 12 January 2008

Abstract
According to the principle introduced in the first two papers of this series, seeking further internal heat integration between reaction operation
and separation operation during the synthesis, design, and operation of a reactive distillation column synthesizing methyl tertiary butyl ether
(MTBE) from methanol and isobutylene is investigated. Although the MTBE reactive distillation column is characterized by complicated
thermodynamic properties and multiple steady states, a substantial reduction of energy requirement and capital investment can still be achieved
with the consideration of further internal heat integration between the reaction operation and the separation operation in the two existing
steady states. Dynamics and operation of the resultant process designs are then examined in terms of static and dynamic analysis and sharp
improvement in process dynamics and controllability is clearly identified through intensive comparison against the simple process design without
the consideration of further internal heat integration between the reaction operation and the separation operation involved. It is demonstrated
that the more synergistic relationship evolved during the reinforcement of internal heat integration should account for the dramatic improvement
in process dynamics and controllability.
䉷 2008 Elsevier Ltd. All rights reserved.

Keywords: Distillation; Internal heat integration; Process synthesis; Process design; Process dynamics; Process control

1. Introduction in the synthesis, design, and operation of some practical reac-

In the first two papers of this series, we investigated the effect
of seeking further internal heat integration between reaction
operation and separation operation in the synthesis, design,
and operation of two hypothetical ideal reactive distillation
columns containing, respectively, a highly exothermic reaction
and a highly endothermic one (Huang et al., 2005, 2006). It has
been demonstrated that in addition to a substantial reduction of
capital investment and operating costs, seeking further internal
heat integration between the reaction operation and the sepa-
ration operation involved can help to improve process dynam-
ics and alleviate the potential difficulties in process operation.
To further ascertain its static and dynamic effect necessitates
certainly the consideration of further internal heat integration
∗ Corresponding author. Tel.: +86 10 64436719; fax: +86 10 64437805.
E-mail address: huangkj@mail.buct.edu.cn (K. Huang).
0009-2509/$ - see front matter 䉷 2008 Elsevier Ltd. All rights reserved.
doi:10.1016/j.ces.2008.01.006
tive distillation systems involving reactions with highly thermal
effect. In this work, a reactive distillation column that
synthesizes methyl tertiary butyl ether (MTBE) from isobuty-
lene (IBUT) and methanol (MEOH) is chosen as an example to
be studied. The MTBE reactive distillation column is character-
ized by an equilibrium-limit reaction with a large amount of re-
action heat released (e.g., HR /HV ,MTBE =37.7/38.02 ≈ 1.0
at P = 1100 kPa and T = 380 K) and therefore appears to be an
appropriate example for examining the effect of internal heat
integration between the reaction operation and the separation
operation upon the process synthesis, design, dynamics and
operation.
Owing to its successful applications in the industrial field
(DeGarmo et al., 1992), the MTBE reactive distillation column
has been extensively studied as one of the textbook examples of
reactive distillation systems over the last 16 years. A great num-
ber of papers have been published, presenting deep insight into
2120 K. Huang et al. / Chemical Engineering Science 63 (2008) 2119 – 2134
the synthesis, design, and operation of the process. A num-
ber of ways were proposed for the effective modeling of the
MTBE reactive distillation column, including the application
of commercial software packages, e.g., Speedup, Aspenplus,
and ChemCad (Abufares and Douglas, 1995; Isla and Irazoqui,
1996; Pilavachi et al., 1997; Bao et al., 2002; Wang et al., 2003).
In particular, the equilibrium and non-equilibrium stage models
were intensively investigated and compared against each other,
and it was clarified that the latter was in general superior to the
former in predicting the unique behaviors of the MTBE reac-
tive distillation column (Baur et al., 1999, 2001a, b; Taylor and
Krishna, 2000; Peng et al., 2002). Input and/or output multi-
plicities were found in this system and have once spurred con-
siderable interests in understanding its formation mechanism
(Jacobs and Krishna, 1993; Nijhuis et al., 1993; Hauan et al.,
1995; Eldarsi and Douglas, 1998a; Mohl et al., 1999; Guttinger
and Morari, 1999a, b; Chen et al., 2000, 2002). Because of the
existence of multiple steady states, transition between different
steady states happened in the dynamic simulation of the MTBE
reactive distillation column (Hauan et al., 1997; Sneesby
et al., 1998; Baur et al., 2001a), giving rise to additional
concern about process operation. Lee and Westerberg (2001)
investigated the synthesis and design of a MTBE reactive dis-
tillation column in terms of a graphical method. They claimed
that the binary azeotrope between isobutylene and methanol
could be circumvented by superimposing the reactive section
onto the feed stage and the rectifying section. Stichlmair and
Frey (2001) addressed the synthesis and design of a MTBE re-
active distillation column in terms of a mixed integer nonlinear
programming (MINLP) formulation. They pointed out the ne-
cessity of taking into account the thermodynamic properties of
the reacting mixture in the establishment of the process super-
structure and found that the thermodynamic efficiency could
be enhanced substantially by adopting a multiple feed scheme
and determining cautiously their corresponding locations in
the reactive section. Daza et al. (2003) suggested designing a
reactive distillation column based on tracking the key compo-
nent generation and studied the design of two MTBE reactive
distillation columns with and without the existence of the inert
component, n-butene, illustrating the great importance of con-
sidering the reaction heat in the process development. Based on
an economical objective function, Eldarsi and Douglas (1998b)
examined the optimum operation of a MTBE reactive distil-
lation column and pointed out that the C4 feed composition
was an important design variable that could significantly affect
the process economics. Wang et al. (2003) investigated the
decentralized control of a MTBE reactive distillation column
and found that simple temperature control could be employed
effectively in the quality control of the bottom product (i.e.,
MTBE). However, a severe oscillation might result by the con-
trol loop that maintained the stoichiometric balance between
isobutylene and methanol, if the latter was used as the manipu-
lated variable. The phenomenon was understood to stem from
the inherent input multiplicities and should be considered seri-
ously in control system synthesis and design. It should be indi-
cated here that almost no systematic study has been conducted
on the relationship between process synthesis and design and
process dynamics and operation for the MTBE reactive distil-
lation column so far. Since complicated process dynamics and
potential operation difficulties are frequently aroused by poor
process synthesis and design for a reactive distillation column,
it is therefore of great significance to consider process dynam-
ics and operation at the early stage of process development.
Seeking further internal heat integration can help to solve
this problem because it attempts to find out a more effective
combination between the reaction operation and the separation
operation involved.
The objective of the current work is to explore the static
and dynamic effect of seeking further internal heat inte-
gration between the reaction operation and the separation
operation upon a reactive distillation column synthesizing
MTBE from isobutylene and methanol. In Section 2, the de-
scription of a typical MTBE reactive distillation column is
presented. After a brief introduction on the principle of in-
ternal heat integration in Section 3, the synthesis and design
of the MTBE reactive distillation columns with and with-
out the consideration of further internal heat integration is
carried out in Sections 4 and 5. Steady state controllability
and closed-loop control are then examined through intensive
comparison between the process designs with and without the
consideration of further internal heat integration in Sections 6
and 7. Some concluding remarks are made on the reinforce-
ment of internal heat integration in the last section of this
article.
2. Process description
As an oxygenated fuel, MTBE served mainly as an important
substitute of lead-based additives to increase the octane num-
ber of gasoline, and the elimination of leaded gasoline once
gave rise to a significant market demand. MTBE is produced
by a reversible exothermic reaction of methanol and isobuty-
lene in the presence of either a heterogeneous catalyst, e.g., a
strong acidic ion exchange resin or a homogeneous catalyst,
2
FMEOH = 198 mol/s dI = 416.65 mol/s
TMEOH = 320 K dII = 405.59 mol/s
4
xNBUT = 0.84
RRI = 7630.13 mol/s
RRII = 2008.80 mol/s
FC4 = 547 mol/s
TC4 = 350 K
11 QREB, I = 133.36 MW
QREB, II = 32.36 MW
16
bI = 172.27 mol/s
bII = 177.53 mol/s
xMTBE = 0.9
Fig. 1. Process design of a MTBE reactive distillation column.
 K. Huang et al. / Chemical Engineering Science 63 (2008) 2119 – 2134 2121

Table 1 Table 2
Nominal operating conditions of the MTBE reactive distillation column in Nominal operating condition of the MTBE reactive distillation column in
steady state I steady state II
Parameter Process design Parameter Process design

2/8/5 2/8(6)/8(3) 2/8/5 2/8(4)/8

Pressure of top stage (kPa) 1100 1100
Pressure drop per stage (kPa) 50 50
No. of stages
Rectifying section 2 2
Reactive section 8 8
Stripping section 5 8
Pressure of top stage (kPa) 1100 1100
Pressure drop per stage (kPa) 50 50
No. of stages
Rectifying section 2 2
Reactive section 8 8
Stripping section 5 8

Liquid holdup (m3 ) Liquid holdup (kmol)

Stage 12.93–17.12 3.28–3.49 Stage 2.87–3.16 1.27–1.50
Condenser 171.17 33.31 Condenser 29.50 14.70
Reboiler 160.68 34.94 Reboiler 31.60 14.95

Feed location of MEOH 4 4 Feed location of MEOH 4 8

Feed pressure of MEOH (kPa) 1114.60 1114.60 Feed pressure of MEOH (kPa) 1114.60 1114.60
Feed thermal condition of MEOH 1.0 1.0 Feed thermal condition of MEOH 1.0 1.0
Feed location of IBUT 11 5 Feed location of IBUT 11 11
Feed pressure of IBUT (kPa) 1114.60 1114.60 Feed pressure of IBUT (kPa) 1114.60 1114.60
Feed thermal condition of IBUT 0. 0.0 Feed thermal condition of IBUT 0.0 0.0
Reflux ratio 18.31 5.56 Reflux ratio 4.95 2.42
Top product composition (NBUT, 0.84 0.84 Top product composition (NBUT, 0.84 0.84
mole fraction) mole fraction)
Top temperature (K) 343.5 343.6 Top temperature (K) 343.60 343.60
Bottom product composition (MTBE, 0.9 0.9 Bottom product composition (MTBE, 0.9 0.9
mole fraction) mole fraction)
Bottom temperature (K) 417.50 414.30 Bottom temperature (K) 415.00 416.01
Conversion rate of isobutylene (mol%) 79.23 83.20 Conversion rate of isobutylene (mol%) 82.17 80.20
Condenser duty (MW) 145.70 48.66 Condenser duty (MW) 44.87 25.81
Reboiler duty (MW) 133.36 36.08 Reboiler duty (MW) 32.36 13.38

e.g., sulfuric acid (Eq. (1)). In this work, the reaction catalyzed
by sulfuric acid is to be investigated. The synthesis of MTBE
often employs a mixed C4 feed of isobutylene and n-butene
which are difficult to separate. Therefore, the MTBE synthesis
can offer an alternative method for separating isobutylene from
n-butene, which has important chemical end users (Clementi
et al., 1979; Stein et al., 2000; Qi et al., 2002; 2004). Reactive
distillation was patented for the MTBE synthesis more than
two decades ago and put into use successfully in the chemical
process industry in 1992 (Smith, 1980; Smith and Huddleston,
1982; DeGarmo et al., 1992). Although the ban on the produc-
tion of MTBE has already taken effect in some countries now
and caused the synthesis and decomposition of MTBE by re-
active distillation systems to be no longer of great significance,
these reactions can still be used as useful examples to inter-
pret the static and dynamic effect of internal heat integration
between the reaction operation and the separation operation of
a reactive distillation column. The results obtained could have
strong implications on the synthesis, design, and operation of
other reactive distillation columns involving reactions with high
thermal effect.
MEOH(CH3 OH) + IBUT(i.C4 H8 ) ↔ MTBE(C5 H12 O),
In this work, a C4 vapor at 350 K (qC4 = 0), comprised of
36 mol% isobutylene and 64 mol% inert n-butene (NBUT),
is employed to react with a pure methanol liquid at 320 K
(qMEOH = 1). As shown in Fig. 1, a basic process design of the
MTBE reactive distillation column is selected to meet the pro-
duction purpose. The process possesses a three sectional config-
uration: 2/8/5 (i.e., a rectifying section, a stripping section, and
a reactive section in between), in addition to a total condenser
at the top and a partial reboiler at the bottom. The top and
bottom products are specified to be 84 and 90 mol% for NBUT
and MTBE, respectively, in order to achieve a conversion rate
of about 80 mol% (in terms of IBUT). It should be indicated
here that because of the existence of the inert component (i.e.,
n-butene), it is impossible to maintain a constant conversion
rate by the product specifications. The simulation of the MTBE
reactive distillation column is carried out using the commercial
ChemCad software and the liquid phase activities are calcu-
lated using the UNIQUAC model with the binary interaction
parameters reported by Rehfinger and Hoffmann (1990). Every
reactive stage is assumed to be in chemical equilibrium, and Eq.
(2) is used to represent the temperature dependence of reaction
equilibrium constant (Al-Jarallah et al., 1988). Other relevant
thermodynamic properties can also be found in these references.

HR,298 = −37.7 MJ/kmol−1 . (1) Ln Keq = −16.33 + 6820/T . (2)

2122 K. Huang et al. / Chemical Engineering Science 63 (2008) 2119 – 2134

420 420
Temperature (K)

Temperature (K)
400 400

380 380

360 360

340 340
1 5 9 13 17 1 5 9 13 17
Stage number Stage number

10000 3000
Liquid flow rate
8000 Liquid flow rate Vapor flow rate
Vapor flow rate
V/L (mol/s)

V/L (mol/s)
6000 2000

4000
1000
2000

0
1 5 9 13 17 0
1 5 9 13 17
Stage number
Stage number

0.9
0.9
IBUT MEOH
Composition (m.f.)

0.72
Composition (m.f.)

IBUT 0.72 MTBE NBUT

0.54 MEOH
MTBE 0.54
0.36 NBUT
0.36
0.18
0.18
0
1 5 9 13 17 0
Stage number 1 5 9 13 17
Stage number
Fig. 2. Profiles of temperature, liquid and vapor flow rates, and liquid com-
position of the MTBE reactive distillation column. Solid line: 2/8(6)/5(3), Fig. 3. Profiles of temperature, liquid and vapor flow rates, and liquid compo-
dashed line: 2/8/5 (steady state I). sition of the MTBE reactive distillation column. Solid line: 2/8(4)/5, dashed
line: 2/8/5 (steady state II).

It is worthwhile to mention here that when catalyzed by sul-
furic acid, it becomes rather difficult to distinguish clearly the
reactive section from the stripping section in the MTBE reac-
tive distillation column (i.e., it is sharply different from the case
catalyzed by the strong acidic ion exchange resin). The homo-
geneous catalyst and the high-boiling reactant, MEOH, are fed
onto the upper column section, while the low-boiling feed, C4
mixture, is introduced onto the lower column section. Normally,
the homogeneous catalyst is primarily distributed in the column
section that is below the MEOH feed location and withdrawn
from the bottom of the process (because it is the least volatile
substance). In spite of this reality, it still appears to be reason-
able to represent the process with a rectifying section/reactive
section/stripping section structure (cf., Fig. 1). Usually, inverse
reactions occur on the bottom part of the process From an equiv-
alent point of view, a stripping section might thus be considered
to exist in the bottom section with no conversion of reactants
(because the forward and backward reactions work against each
other, leading to a zero net conversion rate on these stages).
On the other hand, a stripping section is usually necessitated
to circumvent the side effect of the inverse reactions and helps
to keep the bottom product on its specification. Such a struc-
tural representation may also lend convenience to demonstrate
the effectiveness of seeking further internal heat integration be-
tween the reaction operation and the separation operation on the
thermodynamic efficiency, process dynamics and controllabil-
ity. Although a certain degree of errors, especially in the model-
ing of some practical MTBE reactive distillation columns could
not be avoided, it will give no essential influences at all to the
investigation of the effect of internal heat integration between
the reaction operation and separation operation involved. Fur-
thermore, the simulation result obtained is still of great signifi-
cance to the synthesis and design of MTBE reactive distillation
columns.
 K. Huang et al. / Chemical Engineering Science 63 (2008) 2119 – 2134 2123

150 160
Condenser Reboiler

Heat duty (MW)

Condenser Reboiler

Heat duty (MW)

140 130
130
100
120

110 70
0 1 2 3 4 5 6 0 1 2 3
Stages of ascending C4 feed location Reactive stages superimposed
onto stripping section

130 400

Net reaction rate (mol/s)

2/8/5 2/8(6)/5(3)
200
Heat duty (MW)

110
0
-200
90
Condenser Reboiler -400
70 -600
0 1 2 3 1 5 9 13 17
Reactive stages superimposed Stage number
onto stripping section

Fig. 4. Seeking further internal heat integration in steady state I of the MTBE reactive distillation column: (a) ascent of C4 feed location, (b) superimposition of
reactive stages onto the stripping section in process design, 2/8/5, (c) superimposition of reactive stages onto the stripping section in process design, 2/8(6)/5,
(d) profiles of net reaction rates.

Table 3
Effect of seeking further internal heat integration in the MTBE reactive distillation column (steady state I)
Process design Parameter Evaluations

Process configurations Condenser duty (MW) Reboiler duty (MW) Condenser Reboiler

Basic process design 2/8/5 145.70 133.36 100% 100%

Raising C4 feed location 2/8(6)/5 126.89 114.55 87.09% 85.90%
six stages from the bottom of reactive section
Combinatorial use of the methods 2/8(6)/5(3) 87.33 74.92 59.94% 56.18%
of internal heat integration
Final process design 2/8(6)/8(3) 48.66 36.08 33.40 27.06

3. Process synthesis and design by seeking further
internal heat integration between reaction operation and
separation operation
For a reactive distillation column involving reactions with
highly thermal effect, there usually exist two design strategies
to reinforce internal heat integration between the reaction op-
eration and the separation operation involved. One is to ex-
tend the reactive section to either the rectifying section (in case
of endothermic reactions) or the stripping section (in case of
exothermic reactions) in terms of the detailed reaction system
at hand. The other is to choose deliberately the feed location of
reactant in the reactive section. In the case of a multiple feed
reactive distillation column, thermodynamic analysis should
first be conducted to determine the dominant feed (Dhole and
Linnhoff, 1993). Similar to the case of a conventional distil-
lation column with multiple feeds, the dominant feed location
should be seen as an equivalent point to distinguish the rec-
tifying section from the stripping section. Once the dominant
feed is known, it is then moved up (in case of exothermic reac-
tions)/down (in case of endothermic reactions) to identify the
most appropriate feed location in the reactive section. Both of
these design strategies affect actually the superimposition of re-
active stages onto the separating ones in the rectifying/stripping
section, thereby being able to ascertain an appropriate degree
of internal heat integration (to be more specifically, the way
of combination) between the reaction operation and the sep-
aration operation involved within a number of trial and error
searches. It is worth indicating here the fact that the common
section between the reaction operation and the separation op-
eration should be considered belonging to the reactive section
as well as the rectifying/striping section. It is this common
2124 K. Huang et al. / Chemical Engineering Science 63 (2008) 2119 – 2134
FMEOH = 198 mol/s 2
TMEOH = 320 K
4
5
FC4 = 547 mol/s
TC4 = 350 K
14
19
Fig. 5. Process design with the consideration of further internal heat integration in steady state I.
section that serves to intensify internal heat integration in a reac-
tive distillation column involving reactions with highly thermal
effect.
In terms of the above strategies for strengthening internal heat
integration between the reaction operation and the separation
operation involved, process synthesis and design can be carried
out in a heuristic evolutionary manner for a reactive distilla-
tion column involving reactions with highly thermal effect. At
the beginning, a basic process design without the consideration
of further internal heat integration is first selected based on an
economical objective or rule of thumb. For the simplification of
analysis, the basic reactive distillation column is usually desig-
nated to have three distinct sections (i.e., a rectifying section, a
stripping section, and a reactive section in between) and feeds
of reactants at the ends of the reactive section. With the combi-
natorial utilization of the two methods for reinforcing internal
heat integration between the reaction operation and the separa-
tion operation involved, the distribution of the reactive section
and the location of the dominant feed are searched until the
process configuration with the minimum energy requirement
has been found. If the process design obtained appears to be
satisfactory, then the process synthesis and design is finished,
otherwise, a new basic process design should be chosen and the
above search procedure is repeated. In general, the trial and er-
ror search method appears to be quite robust and effective and
could be employed for the synthesis and design of any reactive
distillation columns involving reactions with highly thermal
effect.
Throughout this work, a unified notation,Nr /Nrea (n2)/
Ns (n1), has been used to represent different process designs
with and without the consideration of further internal heat
integration between the reaction operation and the separation
d = 401.14 mol/s
xNBUT = 0.84
RR = 2229.73 mol/s
QREB = 36.08 MW
b = 180.01 mol/s
xMTBE = 0.9
operation involved. Nr , Nrea , and Ns signify, respectively,
the number of stages in the rectifying, reactive and stripping
sections of a process design. The numbers in the parentheses,
n1 and n2, stand for the superimposition of the reactive sec-
tion onto the stripping section and the movement of the feed
location of the dominant reactant within the reactive section,
respectively. It is further stipulated here that the solid lines
represent uniformly the static and dynamic responses of the
MTBE reactive distillation column developed with the consid-
eration of further internal heat integration between the reac-
tion operation and the separation operation involved, and the
dashed lines the static and dynamic responses of the basic pro-
cess design with the reactive section distributed distinctively
between the rectifying section and the stripping section (i.e.,
without the consideration of further internal heat integration
between the reaction operation and the separation operation
involved).
4. Process synthesis and design without the consideration
of further internal heat integration
In Fig. 1, the reactive section lies distinctively between the
rectifying section and the stripping section and thus no further
internal heat integration has been taken into account between
the reaction operation and the separation operation involved.
Searches for the operating condition that meets the design spec-
ification given were conducted and two steady states (input
multiplicities) were actually found and shown in Tables 1 and
2, respectively. The steady state profiles of temperature, liq-
uid and vapor flow rates, and liquid composition are illustrated
in Figs. 2 and 3, respectively, and sharp difference could be
found in system performance between the steady states I and II,
 K. Huang et al. / Chemical Engineering Science 63 (2008) 2119 – 2134 2125

420 50

40 Condenser Reboiler

Heat duty (MW)

Temperature (K)

400
30
380 20

10
360
0
340 0 1 2 3 4
0 3 6 9 12 15 18 21 Stages of descending MEOH feed location
Stage number

120

Net reaction rate (mol/s)

3000 2/8/5 2/8(4)/5
80
V/L (mol/s)

2000 40

0
1000
Liquid flow rate -40
Vapor flow rate 4 5 6 7 8 9 10 11
0 Stage number
0 3 6 9 12 15 18 21
Stage number Fig. 7. Seeking further internal heat integration in steady state II of the MTBE
reactive distillation column: (a) descent of MEOH feed location, (b) profiles
of net reaction rates.
0.9

0.72
Composition (m.f.)

0.54 feed locations of the two reactants and distribute judiciously

IBUT MEOH
0.36
MTBE NBUT
0.18
0
0 3 6 9 12 15 18
Stage number
Fig. 6. Profiles of temperature, liquid and vapor flow rates, and liquid compo-
sition of the MTBE reactive distillation column (process design: 2/8(6)/8(3)
in steady state I).
yielding, respectively, an overall isobutylene conversion rate
of 79.23 and 82.17 mol%. In the former, although the fresh
feed of MEOH was introduced onto the top of the reactive
section, a much high presence of MEOH was formed ac-
tually in the bottom part of the MTBE reactive distillation
column, hence being unfavorable to the separation opera-
tion between MEOH and MTBE in the stripping section. In
the latter, a high presence of IBUT and NBUT was found
in the bottom part of the MTBE reactive distillation col-
umn and resulted in a very low composition of MEOH in
the reactive section, thereby being not advantageous to the
forward reaction and the separation operation between C4
and MTBE in the stripping section, either. The drawbacks
of the basic process design, 2/8/5, were closely related to
the ineffective combination between the reaction operation
and the separation operation involved. In order to circum-
vent these drawbacks, one has to determine deliberately the
the reactive section along the height of the process during
the synthesis and design of the MTBE reactive distillation
column.
21 5. Process synthesis and design with the consideration of
further internal heat integration
5.1. Seeking further internal heat integration in steady state I
The effect of seeking further internal heat integration be-
tween the reaction operation and the separation operation is
demonstrated in Fig. 4. With the raising of C4 feed location
from the bottom of the reactive section, the heat duties of con-
denser and reboiler decreased monotonically and it appeared
therefore to be advantages to feed C4 mixture at the top part of
the reactive section (Fig. 4a). In terms of the superimposition
of reactive stages onto the stripping section, the heat duties of
condenser and reboiler decreased substantially in comparison
with the basic process design, 2/8/5 (Fig. 4b). For the process
design, 2/8(6)/5, the effect of superimposing additional reac-
tive stages onto the stripping section was examined again and
the results are shown in Fig. 4c. Extremely analogous to the
case of the basic process design, 2/8/5, a substantial reduction
was still found in the heat duties of condenser and reboiler. In
Fig. 4d, the profiles of net reaction rates are compared between
the process designs, 2/8/5 and 2/8(6)/5(3). Here, the net reac-
tion rate is defined as the net difference in the amount of MTBE
between the outlets and inlets of a reactive stage (cf., Eq. (3)).
It is readily understood that seeking further internal heat
2126 K. Huang et al. / Chemical Engineering Science 63 (2008) 2119 – 2134

Table 4
Effect of seeking further internal heat integration in the MTBE reactive distillation column (steady state II)
Process design Parameter Evaluations

Process configurations Condenser duty (MW) Reboiler duty (MW) Condenser Reboiler

Basic process design 2/8/5 44.87 32.36 100% 100%

Lowering MEOH feed location 2/8(4)/5 25.99 13.56 57.92% 41.90%
four stages from the top of reactive section
Final process design 2/8(4)/8 25.81 13.38 57.52% 41.35%

2
d = 413.86 mol/s
xNBUT = 0.84
4
RR = 999.87 mol/s
FMEOH = 198 mol/s
TMEOH = 320 K
8

11
FC4 = 547 mol/s QREB = 13.38 MW
TC4 = 350 K
19

b = 173.19 mol/s
xMTBE = 0.9

Fig. 8. Process design with the consideration of further internal heat integration in steady state II.

integration strengthened the synergistic effect between the re- simultaneously.

action operation and the separation operation involved. Table 3
summarizes the effect of seeking further internal heat inte-
gration between the reactive section and the stripping section.
In comparison with the basic process design, 2/8/5, intro-
ducing C4 feed flow at stage 5 reduced the heat duties of
condenser and reboiler by 12.91% and 14.10%, respectively.
The combinatorial use of the two methods of internal heat
integration (i.e., in 2/8(6)/5(3)) cut down energy requirement
by 40.06% in the condenser and 43.82% in the reboiler. In
Fig. 2, the steady state profiles of temperature, liquid and va-
por flow rates, and liquid composition are also depicted for
the process design, 2/8(6)/5(3). It is readily understood that
the composition of MEOH/IBUT was decreased/increased
in the bottom part of the MTBE reactive distillation column
and this lead to a more favorable distribution of MEOH and
IBUT than in the basic process design, 2/8/5, thereby facil-
itating the reaction operation and the separation operation,
Net reaction rate = Vj yj,MTBE + Lj xj,MTBE
− Vj +1 yj +1,MTBE − Lj −1 xj −1,MTBE .
(3)
Remember the fact that seeking further internal heat integra-
tion reduces actually the driving force of mass transfer in the
rectifying/stripping section where internal heat integration has
been arranged (Melles et al., 2000; Huang and Wang, 2007),
it is therefore necessary to make appropriate compensation for
the MTBE reactive distillation column during process devel-
opment. A straightforward method is to add a number of sep-
arating stages to the stripping section, and this should be de-
termined cautiously in terms of detailed simulation analysis. In
this situation, three stages were added to the stripping section,
giving rise to a final process design, 2/8(6)/8(3). The scheme
of the final process design is shown in Fig. 5, and the nominal
steady state operating condition is also tabulated in Table 1. As
 K. Huang et al. / Chemical Engineering Science 63 (2008) 2119 – 2134 2127

ployed to calculate some design parameters about the column

420 geometry, such as stage diameter, stage spacing, weir height,
downcomer side width, and so forth. The liquid holdups were
400 then estimated based on the determined column geometry. The
Temperature (K)

steady state profiles of temperature, liquid and vapor flow rates,

380 and liquid composition are illustrated in Fig. 6. In comparison
with the basic process design, 2/8/5, the heat duty of reboiler
360 was reduced by 72.94%, in addition to a 66.60% abatement
in the heat duty of condenser (cf., Table 3), thereby securing
340 a simultaneous reduction of capital investment and operating
0 3 6 9 12 15 18 21 cost.
Stage number

1600
5.2. Seeking further internal heat integration in steady state II
Liquid flow rate
Vapor flow rate
1200 Neither the ascent of C4 feed location from the bot-
tom of the reactive section nor did the superimposition
V/L (mol/s)

800 of additional reactive stages onto the stripping section ap-

pear to be effective for the improvement of system per-
400 formance. C4 feed flow was thus considered not to be the
dominant one, and MEOH feed flow should be employed
instead in the reinforcement of internal heat integration
0
0 3 6 9 12 15 18 21 between the reaction operation and the separation opera-
Stage number tion involved. The reactive section was now completely
heat integrated with the stripping section and there was
0.9 only one design option left in this case, i.e., the descent
IBUT MEOH of MEOH feed location. Fig. 7a demonstrates the relation-
0.72
Composition (m.f.)

MTBE NBUT
0.54
0.36
0.18
0 net reaction rates for the two process configurations: 2/8/5 and
0 3 6 9 12 15 18
Stage number
Fig. 9. Profiles of temperature, liquid and vapor flow rates, and liquid com-
position of the MTBE reactive distillation column (process design: 2/8(4)/8
in steady state II).
can be seen, the overall isobutylene conversion rate underwent
a small change from 79.23% in the basic process design, 2/8/5,
to 83.20% in the process design, 2/8(6)/8(3), implying the pos-
itive effect from the reinforcement of internal heat integration
in this situation. Furthermore, the liquid holdups on stages (in-
cluding those in the top condenser and bottom reboiler) were
substantially reduced (by a factor ranging from 3.94 to 514)
after the reinforcement of internal heat integration between the
reaction operation and the separation operation involved, im-
plying the paramount importance of process synthesis and de-
sign to the efficacy of process intensification. Here, the sizing
of the MTBE reactive distillation column was carried out with
the built-in function of the ChemCad software. In particular, the
criterion that the flood percent on each stage was not allowed
to exceed 70% at the nominal operating conditions was em-
ship between MEOH feed location and the heat duties of
condenser and reboiler. A steady improvement in system
performance was noticed when MEOH feed location was
lowered from stage 4 of the basic process design. To well
understand this phenomenon, one needs to examine the profile
of net reaction rates, and Fig. 7b compares the profiles of the
21
2/8(4)/5. As can be seen, the reaction occurred mainly at the
top of the reactive section in the basic process design, 2/8/5.
In particular, backward reaction happened on the last three
reactive stages, representing a kind of adverse internal heat in-
tegration between the reactive section and the stripping section.
This unfavorable distribution of the net reaction rates was ap-
parently caused by the inappropriate determination of MEOH
feed location. More specifically, MEOH feed location was
raised actually too many plates from the bottom of the re-
active section. After the adjustment of MEOH feed location,
the drawback of the basic process design was alleviated,
substantially. The reaction took place now primarily in the
middle and at the bottom of the reactive section and no back-
ward reaction happened at all in the process design, 2/8(4)/5.
Although adverse internal heat integration occurred on the
reactive stages above the MEOH feed location, its negative
effect appeared to be smaller than the positive one of inter-
nal heat integration below the MEOH feed location. Table 4
sums up the effect of seeking further internal heat integra-
tion between the reactive section and the stripping section.
In comparison with the basic process design, 2/8/5, introduc-
ing MEOH feed flow at stage 8 reduced the heat duties of
condenser and reboiler by 42.08% and 58.10%, respectively.
2128 K. Huang et al. / Chemical Engineering Science 63 (2008) 2119 – 2134

Table 5
Relative gain array for the process designs, 2/8/5 (a) and 2/8(6)/8(3) (b), in
steady state I 2 LC
FMEOH 4
Controlled variable Manipulated variable
QREB RR FMEOH

(a) d, xNBUT
8 TC
T8 34.94 −34.97 1.03 FC
10
T10 −23.96 27.59 −2.63 TC
11
T17 −9.98 8.38 2.60
FC4
(b) Manipulated variable
RR FMEOH QREB 16

T6 2.71 −0.51 −1.20 LC

T14 −2.41 1.99 1.42 TC b, xMTBE
T16 0.70 −0.48 0.78

Table 6
Relative gain array for the process designs, 2/8/5 (a) and 2/8(4)/8 (b), in 2 LC
steady state II FMEOH 4
Controlled variable Manipulated variable 6
TC
RR FMEOH QREB
d, xNBUT
(a)
T4 0.54 0.57 −0.11 FC
T14 43.83 3.02 −45.85 TC 14
T16 −43.37 −2.59 46.96 FC4 16
TC
(b) 19
T7 1.84 0.05 −0.89 LC
T10 0.90 0.94 −0.84
b, xMTBE
T16 −1.74 0.1 2.73

It should be indicated here that the overall isobutylene con-
version rate decreased to 80.28% in the process design,
2/8(4)/5, from 82.17% in the basic process design, 2/8/5.
Although it really influenced system performance, its effect
appeared to be extremely small as compared with the re-
duction of energy requirement obtained. Therefore, seeking
further internal heat integration was no doubt the primary
reason that rendered the dramatic improvement in system
performance. In Fig. 3, the steady state profiles of tempera-
ture, liquid and vapor flow rates, and liquid composition are
also depicted for the process design, 2/8(4)/5. It is readily
understood that the presence of IBUT was lowered and a
higher distribution of MEOH was now formed in the reac-
tive section than in the process design, 2/8/5, thereby ben-
efiting the reaction operation and the separation operation,
simultaneously.
To compensate the reduction in the mass transfer driving
forces, three stages were also added to the stripping section,
leading to a final process design, 2/8(4)/8. The scheme of the
final process design is illustrated in Fig. 8, and the nomi-
nal steady state operating condition is also listed in Table 2.
The liquid holdups on stages (including those in the top con-
denser and bottom reboiler) were again substantially reduced
(by a factor ranging from 2.0 to 23) after the reinforcement of
Fig. 10. Control schemes of the MTBE reactive distillation column in steady
state I: (a) 2/8/5, (b) 2/8(6)/8(3).
internal heat integration between the reaction operation and
the separation operation involved. The steady state profiles of
temperature, liquid and vapor flow rates, and liquid compo-
sition are illustrated in Fig. 9. In comparison with the basic
process design, 2/8/5, the heat duty of reboiler was reduced
by 58.65%, in addition to a 42.48% abatement in the heat
duty of condenser (cf., Table 4), thereby securing again a si-
multaneous reduction of capital investment and operating cost.
6. Steady state controllability analysis
6.1. Steady state controllability analysis in steady state I
The keys to controlling a reactive distillation column in
which the reaction is equilibrium limited are to maintain
the product composition as well as the stoichiometric bal-
ance between the feeds of reactants. Temperature control is
used in the study to accomplish these control keys, and sin-
gular value decomposition method (SVD) is used to select
the controlled stage temperatures (Luyben, 2006) Based on
 K. Huang et al. / Chemical Engineering Science 63 (2008) 2119 – 2134 2129

for the basic process design, 2/8/5, and the temperatures

of stages, 7, 10, and 16 for the process design, 2/8(4)/8.
2 LC The RGA is shown in Table 6 for these process designs.
FMEOH 4 It can be readily seen that the former was inferior to the
TC
latter in the aspect of process controllability and the sensi-
tivity to process uncertainties, implying again the positive
d, xNBUT
FC
effect from the reinforcement of internal heat integration be-
11
tween the reaction operation and the separation operation
FC4 involved.
14
TC
16 TC
LC 7. Closed-loop control
b, xMTBE
7.1. Control system design

A decentralized temperature control system is employed

2 LC
4
7 the multiplicity between the controlled and manipulated
TC
FMEOH •8
d, xNBUT
10
FC4 TC 11
FC 16
TC
19
LC
b, xMTBE
Fig. 11. Control schemes of the MTBE reactive distillation column in steady
state II: (a) 2/8/5, (b) 2/8(4)/8.
the SVD method, the temperature of stages, 8, 10, and 17
were selected as the controlled variables for the basic pro-
cess design, 2/8/5, and the temperatures of stages, 6, 14, and
16 for the process design, 2/8(6)/8(3). The manipulated vari-
ables are the reflux flow rate, methanol feed flow rate, and
reboiler heat duty. Relative gain array (RGA) was calculated
and shown in Table 5 for these process designs. Based on
the RGA, one can readily find that a less degree of inter-
actions between these control loops and thus much better
controllability were resulted in 2/8(6)/8(3) than in 2/8/5.
Since the magnitude of the RGA elements is also a good
indication of the sensitivity to process uncertainties, the dra-
matic reduction in the size of the RGA elements pointed
out the fact that the sensitivity to process uncertainties was,
by a certain extent, suppressed after the reinforcement of
internal heat integration in the MTBE reactive distillation
column.
6.2. Steady state controllability analysis in steady state II
Likewise, the temperatures of stages, 4, 14, and 16 were
selected by the SVD method as the controlled variables
for the operation of the MTBE reactive distillation column.
Because of the existence of multiple steady states in the
MTBE reactive distillation column, one of the primary ob-
jectives in control system synthesis and design is to avoid
variables. Through a large amount of steady state analy-
sis, C4 was found to be the better manipulated variable
than MEOH for the throughput control (i.e., production rate
handle). The control configurations were devised in accor-
dance with the RGA analysis in Section 6 and sketched in
Figs. 10 and 11 for the steady states I and II, respectively.
It is worth mentioning here that the control configurations
became quite different before and after seeking further in-
ternal heat integration between the reaction operation and
the separation operation involved due to the great varia-
tions caused in the temperature profiles. In Fig. 10, while
the temperatures of stages 8, 10, and 17 were controlled
by manipulating the heat duty of reboiler, the reflux flow
rate, and the feed flow rate of methanol, respectively, for
the basic process design, 2/8/5, the temperatures of stages
6, 14, and 16 were controlled by manipulating the reflux
flow rate, the feed flow rate of methanol, and the heat duty
of reboiler, respectively, for the process design, 2/8(6)/8(3).
In Fig. 11, while the temperatures of stages 4, 14, and 16
were controlled by manipulating the reflux flow rate, the
feed flow rate of methanol, and the heat duty of reboiler,
respectively, for the basic process design, 2/8/5, the temper-
atures of stages 7, 10, and 16 were controlled by manipu-
lating the reflux flow rate, the feed flow rate of methanol,
and the heat duty of reboiler, respectively, for the process
design, 2/8(4)/8. The levels of the reflux-drum and the bot-
tom reboiler were controlled by the distillate and bottom
product flow rates, respectively. The dynamics of tempera-
ture measurements was assumed to be a first-order lag of
30 s and all control valves were designed to be half open at
the nominal steady state. Proportional-only (P) controllers
were used for all the level control loops and proportional
plus integral (PI) controllers were adopted for the three
temperature control loops. The PI controllers were tuned
in terms of an experimental design approach proposed by
Finco et al. (1987).
2130 K. Huang et al. / Chemical Engineering Science 63 (2008) 2119 – 2134

0.4 1
0.2 stage 6 stage 8 0.5

ΔT (K)

ΔT (K)
stage 10 stage 14
0 0
-0.2 -0.5
-0.4 -1
0 10 20 30 0 10 20 30
Time [h] Time [h]
4 8000
2

RR (mol/s)
6000
ΔT (K)

0
-2 4000
stage 16 stage 17
-4 2000
0 10 20 30 0 10 20 30
Time [h] Time [h]
215 140
FMEOH (mol/s)

QREB (MW)
205
100
195
60
185
175 20
0 10 20 30 0 10 20 30
Time [h] Time [h]
0.86 0.95
xNBUT (m.f.)

0.85
xMTBE (m.f.)

0.92
0.84
0.83 0.89
0.82
0 10 20 30 0.86
Time [h] 0 10 20 30
Time [h]

Fig. 12. Closed-loop responses to a ±0.01 step change in the MTBE composition of the bottom product (steady state I).

7.2. Closed-loop operation in steady state I
In Fig. 12, the closed-loop responses are compared be-
tween the process designs, 2/8/5 and 2/8(6)/8(3), when step
changes of appropriate magnitudes are introduced simulta-
neously to the set-points of the top, reactant stoichiometry,
and bottom control loops in order to bring about a step
change of ±0.01 in the bottom composition of MTBE, re-
spectively. It is noted that the basic process design, 2/8/5,
failed to accomplish a smooth transition to the desired
steady states and was characterized by a very long settling
time (?30 h). In addition to the great overshoots exhib-
ited in the bottom product, a high degree of interactions
was observed in the top product, leading to the exis-
tence of relatively large deviations in the product quality.
As far as the process design, 2/8(6)/8(3), was concerned,
fairly smooth transition was achieved, with almost no over-
shoots in the bottom product, relatively small settling times
(around 15 h), and a tolerable degree of interactions to the
top product. The drastic improvement in the closed-loop
operation indicates the positive effect of seeking further
internal heat integration between the reaction operation and
the separation operation upon the process dynamics and
controllability.
In Fig. 13, the closed-loop responses are compared be-
tween the process designs, 2/8/5 and 2/8(6)/8(3), when a step
change of ±10% is introduced, respectively, to the feed flow
rate of C4 (i.e., throughput changes). The former displayed
again much large deviations in the controlled temperatures
and the bottom product composition. Although the control
system could finally restore the process to the desired steady
state, a very long time was actually needed (?30 h). On the
contrary, the latter exhibited much smaller deviations than the
former in the controlled temperatures and the bottom product
composition with a dramatically reduced settling time (around
22 h). Although relatively larger deviations in the top prod-
uct composition than those of the former were found in the
first 18 hs, the reverse is true after that time instant. Almost
no steady state discrepancies could be found in the top and
bottom products. The drastic improvement in the closed-loop
operation confirms again the positive effect of seeking fur-
ther internal heat integration between the reaction operation
 K. Huang et al. / Chemical Engineering Science 63 (2008) 2119 – 2134 2131

0.4 1
stage 6 stage 8 stage 10 stage 14
0.2 0.5

ΔT (K)
ΔT (K)
0 0
-0.2 -0.5
-0.4 -1
0 10 20 30 0 10 20 30
Time [h] Time [h]
4 8000
2 6000

RR (mol/s)
ΔT (K)

0 4000
stage 16 stage 17
-2 2000
-4 0
0 10 20 30 0 10 20 30
Time [h] Time [h]
225 140
FMEOH (mol/s)

215

QREB (MW)
100
205
195 60
185
175 20
0 10 20 30 0 10 20 30
Time [h] Time [h]
0.87 0.95
xNBUT (m.f.)

0.92
xMTBE (m.f.)

0.85
0.89
0.83
0.86
0.81
0 10 20 30 0.83
Time [h] 0 10 20 30
Time [h]

Fig. 13. Closed-loop responses to a ±10% step change in the feed flow rate of C4 (steady state I).

and the separation operation upon the process dynamics and
controllability.
7.3. Closed-loop operation in steady state II
In Fig. 14, the closed-loop responses are compared be-
tween the process designs, 2/8/5 and 2/8(4)/8, when step
changes of appropriate magnitudes are introduced simulta-
neously to the set-points of the top, reactant stoichiometry,
and bottom control loops in order to arouse a step change of
±0.01 in the bottom composition of MTBE, respectively. As
can be seen, the basic process design, 2/8/5, with a greater
degree of interactions to the top product quality, showed
slower transitions to the desired steady states than, 2/8(4)/8.
While a certain degree of steady state discrepancies were
observed in the top and bottom products in the former, al-
most no steady state discrepancies could be found in the
latter.
In Fig. 15, the closed-loop responses are compared be-
tween the process designs, 2/8/5 and 2/8(4)/8, when a step
change of ±10% is introduced, respectively, to the feed
flow rate of C4. While a somewhat similar degree of max-
imum deviations was displayed in the top product compo-
sition between the process designs, 2/8/5 and 2/8(4)/8, the
former presented larger maximum deviations than the lat-
ter in the bottom product composition. In particular, much
longer settling times were experienced by the former than
by the latter. Again, a certain degree of steady state dis-
crepancies were observed in the top and bottom products in
the former and almost no steady state discrepancies could
be found in the latter. The improvement in the closed-loop
operation under MTBE purity and C4 feed flow changes
evidences again the positive effect of seeking further in-
ternal heat integration between the reaction operation and
the separation operation upon the process dynamics and
controllability.
7.4. Dynamic effect of the reduction of liquid holdups
It is interesting to consider why the settling times of
control systems were reduced substantially after seeking
further internal heat integration between the reaction oper-
ation and the separation operation involved. Although the
reduction of liquid holdups contributed somehow to the
2132 K. Huang et al. / Chemical Engineering Science 63 (2008) 2119 – 2134

0.3 1.5
stage 4 stage 7

0.1 0.5 stage 10 stage 14

ΔT (K)
ΔT (K)
-0.1 -0.5

-0.3 -1.5
0 10 20 30 0 10 20
30
Time [h] Time [h]
4 2300
2

RR (mol/s)
1800
ΔT (K)

0 stage 16 stage 16

-2 1300

-4 800
0 10 20 30 0 10 20 30
Time [h] Time [h]
205 36
FMEOH (mol/s)

30

QREB (MW)
200
24
195
18
190 12
0 20 0 10 20 30
10 30
Time [h] Time [h]
0.86 0.92
xNBUT (m.f.)

0.85 0.91
xMTBE (m.f.)

0.84 0.9
0.83
0.89
0.82
0 10 20 30 0.88
0 10 20 30
Time [h]
Time [h]

Fig. 14. Closed-loop responses to a ±0.01 step change in the MTBE composition of the bottom product (steady state II).

occurrence of this phenomenon, it is only ranked as the ing mixture and the strong interaction between the reac-
secondary reason. The primary reason stemmed actually tion operation and the separation operation involved, these
from the reinforcement of internal heat integration, which results are found to be in good accordance with those ob-
brought about not only the reduction of liquid holdups, tained in the first two papers of this series in terms of
but also a refined relationship between the reaction oper- two hypothetical ideal reactive distillation columns contain-
ation and the separation operation involved. The refined ing, respectively, a highly exothermic reaction and a highly
relationship was responsible for the substantial reduction endothermic one. The reason can be solely attributed to
of the settling times because the internal conflicts were the fact that seeking further internal heat integration has
alleviated. lead actually to a well-coordinated relationship between the
reaction operation and the separation operation involved
during the trial and error search in the process synthesis
8. Conclusion and design. It evidences again the great importance of consid-
ering further internal heat integration in the development of
The synthesis, design, and operation of a MTBE reac- reactive distillation columns involving reactions with highly
tive distillation column have been conducted in this work. thermal effect.
It has been found that seeking further internal heat integra- Future work will be centered on the synthesis, design,
tion between the reaction operation and the separation op- and control studies of more complicated reactive distillation
eration involved can really yield a substantial improvement columns involving reactions with highly thermal effect (e.g., in
in the thermodynamic efficiency besides a drastic reduc- the presence of multiple reactions and/or the existence of side
tion of capital investment. Furthermore, favorable influences reactions). Experimental-based examination of internal heat
have been acquired on the process dynamics and control- integration between the reaction operation and the separation
lability with this strategy of process development. In spite operation involved in a reactive distillation column is also an
of the complicated thermodynamic properties of the react- important subject in the future.
 K. Huang et al. / Chemical Engineering Science 63 (2008) 2119 – 2134 2133

0.9 2.5
stage 4 stage 7 stage 10 stage 14
1.5
0.3

ΔT (K)
ΔT (K)
0.5
-0.3 -0.5
-1.5
-0.9 -2.5
0 10 20 30 0 10 20 30
Time [h] Time [h]
9 2300
stage 16 stage 16

RR (mol/s)
4 1800
ΔT (K)

-1 1300

-6 800
0 10 20 30 0 10 20 30
Time [h] Time [h]
230 40

QREB (MW)
FMEOH (mol/s)

210 30

190 20

170 10
0 10 20 30 0 10 20 30
Time [h] Time [h]
0.86 0.92
0.85 0.91
xNBUT (m.f.)

xMTBE (m.f.)

0.84 0.9
0.83 0.89
0.82 0.88
0 10 20 30 0 10 20 30
Time [h] Time [h]

Fig. 15. Closed-loop responses to a ±10% step change in the feed flow rate of C4 (steady state II).

Notation x liquid composition

y vapor composition
b bottom withdrawal, kmol s−1 Greek letter
d distillate flow rate, kmol s−1
 variation
F feed flow rate of a reactant, kmol s−1
Subscripts
FC flow rate controller
HR reaction heat, kJ kmol−1 b bottom product
HV latent heat, kJ kmol−1 d distillate
Keq equilibrium constant IBUT isobutylene
L liquid flow rate, kmol s−1 j stage index
LC level controller MEOH methanol
n number of stages MTBE methyl tertiary butyl ether
N number of stages NBUT n-butene
P pressure, Pa r rectifying section
PI proportional plus integral controller rea reactive section
q feed thermal condition REB reboiler
Q heat duty, W s stripping section
RR reflux flow rate, kmol s−1
SVD singular value decomposition Acknowledgments
T temperature, K
TC temperature controller We are truly indebted to the anonymous reviewers who
V vapor flow rate, kmol s−1 helped us a lot in the revision of the paper. The first author
2134 K. Huang et al. / Chemical Engineering Science 63 (2008) 2119 – 2134

is also grateful to Dr. Hiroyuki Kodama and Dr. Yoshihiko Huang, K., Wang, S.J., 2007. Design and control of a MTBE decomposition
Nagata (Research Institute for Human Science and Biomedical reactive distillation column. Industrial and Engineering Chemistry Research
Engineering of the National Institute of Advanced Industrial 46, 2508–2519.
Huang, K., Iwakabe, K., Nakaiwa, M., Tsutsumi, A., 2005. Towards further
Science and Technology (AIST) of Japan) for their valuable internal heat integration in design of reactive distillation columns—part I:
comments. The project is financially supported by the Na- the design principle. Chemical Engineering Science 60, 4901–4914.
tional Science Foundation of China under the contract no. of Huang, K., Nakaiwa, M., Tsutsumi, A., 2006. Towards further internal heat
20776011. integration in design of reactive distillation columns—part II: the process
dynamics and operation. Chemical Engineering Science 61, 5377–5392.
References Isla, M.A., Irazoqui, H.A., 1996. Modeling, analysis, and simulation of
a methyl tert-butyl ether reactive distillation column. Industrial and
Engineering Chemistry Research 35, 2696–2708.
Abufares, A.A., Douglas, P.L., 1995. Mathematical modeling and simulation
Jacobs, R., Krishna, R., 1993. Multiple solutions in reactive distillation for
of an MTBE catalytic distillation process using speedup and aspenplus.
methyl-tert-butyl-ether synthesis. Industrial and Engineering Chemistry
Chemical Engineering Research and Design 73A, 3–12.
Research 32, 1706–1709.
Al-Jarallah, A.M., Lee, A.K.K., Aiddiqui, M.A.B., 1988. Kinetics of methyl
Lee, J.W., Westerberg, A.W., 2001. Graphical design applied to MTBE
tertiary butyl ether synthesis catalyzed by sulphuric acid. Chemical
and methyl acetate reactive distillation processes. A.I.Ch.E. Journal 47,
Engineering Journal 39, 169–174.
1333–1345.
Bao, J., Gao, B., Wu, X., Yoshimoto, M., Nakao, K., 2002. Simulation
Luyben, W.L., 2006. Evaluation of criteria for selecting temperature control
of industrial catalytic-distillation process for production of methyl tert-
trays in distillation columns. Journal of Process Control 16, 115–134.
butyl ether by developing user’s model on aspenplus platform. Chemical
Melles, S., Grievink, J., Schrans, S.M., 2000. Optimization of the conceptual
Engineering Journal 90, 253–266.
design of reactive distillation columns. Chemical Engineering Science 55,
Baur, R., Higler, A.P., Taylor, R., Krishna, R., 1999. Comparison of
2089–2097.
equilibrium stage and non-equilibrium stage models for reactive distillation.
Mohl, K.D., Kienle, A., Gilles, E.D., Rapmund, P., Sundmacher, K.,
Chemical Engineering Journal 76, 33–47.
Hoffman, U., 1999. Steady-state multiplicities in reactive distillation
Baur, R., Taylor, R., Krishna, R., 2001a. Dynamic behavior of reactive
columns for the production of fuel ethers MTBE and TAME: theoretical
distillation tray columns described by a non-equilibrium cell model.
analysis and experimental verification. Chemical Engineering Science 54,
Chemical Engineering Science 56, 1721–1729.
1029–1043.
Baur, R., Higler, A.P., Taylor, R., Krishna, R., 2001b. Dynamic behavior of
Nijhuis, S.A., Kerholf, F.P.J.M., Mak, A.N.S., 1993. Multiple steady
reactive distillation columns described by non-equilibrium stage models.
states during reactive distillation of methyl-tert-butyl-ether. Industrial and
Chemical Engineering Science 56, 2085–2102.
Engineering Chemistry Research 32, 2767–2774.
Chen, F., Huss, R.S., Malone, M.F., Doherty, M.F., 2000. Simulation of
Peng, J., Lextrait, S., Edgar, T.F., Eldridge, R.B., 2002. A comparison
kinetics effects in reactive distillation. Computers & Chemical Engineering
of steady-state equilibrium and rate-based models for packed reactive
24, 2457–2472.
distillation columns. Industrial and Engineering Chemistry Research 41,
Chen, F., Huss, R.S., Malone, M.F., Doherty, M.F., 2002. Multiple steady
2735–2744.
states in reactive distillation: kinetics effects. Computers & Chemical
Pilavachi, P.A., Schenk, M., Perez-Cisneros, E., Gani, R., 1997. Modeling and
Engineering 26, 81–93.
simulation of reactive distillation operations. Industrial and Engineering
Clementi, A., Oriani, G., Ancillotti, F., Pecci, G., 1979. Upgrade C4’s with
Chemistry Research 36, 3188–3197.
MTBE process. Hydrocarbon Processing 58, 109–113.
Qi, Z., Sundmacher, K., Stein, E., Kienle, A., Kolah, A., 2002. Reactive
Daza, O.S., Perez-Cisneros, E.S., Bek-Pedersen, E., Gani, R., 2003. Graphical
separation of isobutene from C4 crack fraction by catalytic distillation
and stage-to-stage methods for reactive distillation column design.
processes. Separation and Purification Technology 26, 147–163.
A.I.Ch.E. Journal 49, 2822–2841.
Qi, Z., Kienle, A., Mohl, K.D., Tuchlenski, A., Sundmacher, K., 2004. MTBE
DeGarmo, J.L., Parulekar, V.L., Pinjala, V., 1992. Consider reactive
decomposition in a reactive distillation column. Chemical Engineering
distillation. Chemical Engineering Progress 88, 43–50.
Research and Design 82A, 185–191.
Dhole, V.R., Linnhoff, B., 1993. Distillation column targets. Computers &
Rehfinger, A., Hoffmann, U., 1990. Kinetics of methyl tertiary butyl ether
Chemical Engineering 17, 549–560.
liquid phase synthesis catalyzed by ion exchange resin—I. Intrinsic rate
Eldarsi, H.S., Douglas, P.L., 1998a. Methyl-tert-butyl-ether catalytic
expression in liquid phase activities. Chemical Engineering Science 45,
distillation column: multiple steady states. Chemical Engineering Research
1605–1617.
and Design 76A, 509–516.
Smith, L.A., 1980. Catalytic distillation process and catalyst. European Patent
Eldarsi, H.S., Douglas, P.L., 1998b. Methyl-tert-butyl-ether catalytic
Application, EP8860.
distillation column. Part II: optimization. Chemical Engineering Research
Smith, L.A., Huddleston, M.N., 1982. New MTBE design now commercial.
and Design 76A, 517–524.
Hydrocarbon Processing 61, 121–123.
Finco, M., Luyben, W.L., Polleck, R.E., 1987. Control of distillation
Sneesby, M.G., Tade, M.O., Smith, T.N., 1998. Steady state transitions in the
columns with low relative volatilities. Industrial and Engineering Chemistry
reactive distillation of MTBE. Computers & Chemical Engineering 22,
Research 28, 75–83.
879–892.
Guttinger, T.E., Morari, M., 1999a. Predicting multiple steady states
Stein, E., Kienle, A., Sundmacher, K., 2000. Separation using coupled reactive
in equilibrium reactive distillation. I. Analysis of nonhybrid systems.
distillation column—a case study. Chemical Engineering 107, 68–72.
Industrial and Engineering Chemistry Research 38, 1633–1648.
Stichlmair, J., Frey, T., 2001. Mixed integer nonlinear programming
Guttinger, T.E., Morari, M., 1999b. Predicting multiple steady states in
optimization of reactive distillation processes. Industrial and Engineering
equilibrium reactive distillation. II. Analysis of hybrid systems. Industrial
Chemistry Research 40, 5978–5982.
and Engineering Chemistry Research 38, 1649–1665.
Taylor, R., Krishna, R., 2000. Modeling reactive distillation. Chemical
Hauan, S., Hertzberg, T., Lien, K.M., 1995. Why methyl tert-butyl ether
Engineering Science 55, 5183–5229.
product by reactive distillation may yield multiple solution. Industrial and
Wang, S.J., Wong, D.S.H., Lee, E.K., 2003. Effect of interaction multiplicity
Engineering Chemistry Research 34, 987–991.
on control system design for a MTBE reactive distillation column. Journal
Hauan, S., Schrans, T., Lien, K.M., 1997. Dynamic evidence of the multiplicity
of Process Control 13, 503–515.
in methyl tert-butyl ether reactive distillation. Industrial and Engineering
Chemistry Research 36, 987–991.