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Review

Reactive Distillation Processes


By Johann Stichlmair and Thomas Frey*

Reactive distillation, i. e. the simultaneous implementation of reaction and distillation in a counter currently operated column, ia
a promising alternative to the common sequential processes. In a preceding paper the effective phase equilibrium of a reactive
distillation has been studied with a special focus on the determination of so called reactive azeotropes. In this contribution
knowledge of these thermodynamic fundamentals is applied to the conceptual design of reactive distillation processes.
Furthermore, some process examples of technical importance are presented.

Reactive distillation is the simultaneous implementation of For nonreactive distillation, the column mass balance is a
reaction and distillation within a countercurrent column. A straight line containing the feed FÇ, the distillate D Ç and the
preceding publication [1] focused on the thermodynamics of bottom product B Ç . For reactive distillation, this holds true only
reactive distillation. It was shown that a system's phase if the reaction conditions are projected along stoichiometric
equilibrium can be represented by so-called reactive distilla- lines into reaction-free conditions [1].
tion lines that enable the determination of possible products. Possible separation inhibitors are azeotropes, border
Hence, knowledge of reactive distillation lines is the basis distillation lines and border distillation planes. The effective-
required for the design of such processes. An important ness of reactive distillation is based on its ability to cross
boundary condition is the existence of reactive azeotropes nonreactive distillation boundaries. However, a disadvantage
which occur when the concentration change due to distillation exists in that it can often add boundaries, e.g., reactive
is compensated for by the concentration change resulting from azeotropes or reactive border distillation lines, which deterio-
the chemical reaction. Reactive azeotropes are reactive rate the separation process.
distillation inhibitors. Reactive distillation is highly efficient when applied to
This paper will demonstrate how knowledge of reactive catalytic reactions, as it is possible to combine the distillation
distillation lines and potential reactive azeotropes can be used and reaction zones within a column. In the reaction zone,
for the systematic design of reactive distillation processes. To nonreactive azeotropes can be overcome; in the nonreactive
begin with, a general approach will be presented using systems zone, reactive azeotropes can be overcome. If possible, a
with varying reaction mechanisms. This will then be followed heterogeneous catalyst should be applied to avoid the often
by several well-known processes of technical importance. laborious separation associated with a homogeneous catalyst.
This work presents the possibilities of reactive distillation in
a general way, through the comparison of conventional
1 Topology of Reactive Distillation Processes processes and reactive distillation processes.

As previously stated, knowledge of reactive distillation lines


1.1 Synthesis Reaction with a Single Product
facilitates the design of reactive distillation processes. The
methodology required is identical to that used for the design of First, we consider reactions consisting of two reactants and
nonreactive distillation processes [2]. The main steps are as resulting in one product, which do not reach complete
follows: equilibrium. The pure substances are denoted as a, b and c
l Determination of possible products or of feasible separa- according to rising boiling temperature, i.e., a denotes the low
tion regions; boiler. According to this notation, the reaction mechanism is
l Consideration of the column mass balance; written as follows:
l Identification of possible separation borders, e.g., azeo-
xc
tropes or border distillation lines. a + b « c with KR = (1)
xa xb
The possible products are determined from knowledge of
the existing concentration profiles within the column. Furthermore, it is assumed that a minimum azeotrope
Reactive distillation lines represent these concentration occurs between components b and c resulting in a border
Ç and the bottom product B
profiles, i.e., the distillate D Ç must distillation line which runs towards the low boiler a.
lie on the same distillation line for large reflux ratios. Fig. 1A shows the conventional process with sequential
implementation of reaction and distillation. A mixture ab is
± fed into the reactor R-1, where the reaction takes place
[*] Prof. Dr.-Ing. J. Stichlmair, Dipl.-Ing. Th. Frey, Lehrstuhl A für reaching equilibrium in the presence of a catalyst. In a
Verfahrenstechnik, Technische Universität München, Boltzmannstr. 15,
D-885748 Garching, Germany. subsequent distillation column, pure component c is separated

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the upper zone, the concentration profile always lies on the


chemical equilibrium line, i.e., on the reactive distillation line.
However, in the lower part, the concentration profile
approaches that of a distillation line that begins at the high
boiler c. The occurring distillation boundary becomes insig-
nificant if an appropriate reactive zone location is chosen.
The main advantage of reactive distillation is the removal of
the recycling stream; in fact, an effective recycling takes place
within the column. For exothermic reactions, another im-
portant advantage is that the heat of reaction does not have to
be removed from the reaction zone, but can immediately be
used in the distillation zone.

1.2 Decomposition Reactions with Two Products

An important class of reactions are decomposition reac-


tions, having the following reaction mechanism:
xa xb
c « a + b with KR = (2)
Figure 1A. Process with sequential implementation of the reaction a + b « c and xc
distillation in a system with a border distillation line.
Decomposition reactions are often endothermic. In most
as the bottom product B Ç 1 from the reactor effluent R
Ç 1, and the
cases, the products a and b have to be separated in pure form
Ç 1 is recycled back into the reactor. Due to the
distillate D for further processing.
existing distillation boundary, the distillate D Ç 1 contains a
Fig. 2A presents the conventional process with sequential
considerable amount of high boiler c, moving the reaction implementation of reaction and distillation. Catalytic conver-
equilibrium to the left, i.e., reducing conversion. If the sion takes place within the reactor R-1, and the feed is split
reaction equilibrium lies very close to the distillation into components a, b and c. The ternary reactor effluent B Ç 1 is
boundary, a large mass stream must be recycled, resulting in then fed into the column C-1, where component c is separated
a very uneconomical process. Ç 1 is fed into
and recycled back into the reactor. The distillate D
Fig. 1B presents the simultaneous implementation of a second column C-2 and separated into its pure substances a
reaction and distillation in a single column. As it is assumed and b.
that the unconverted reactants a and b are more volatile than
the product c, they move upwards within the column. If a
catalyst is present in this upper zone, a further chemical
conversion will occur. Thus, for the case of stoichiometric
composition of the reactants with an appropriately large
reflux ratio, complete reactant conversion can be reached in
the upper region of the column. In the lower region of the
column, the high boiler c is separated as pure product by
simple distillation, i.e., in the absence of a catalyst. The
triangular diagram in Fig. 1B represents the concentration
profile within the column. Due to the presence of a catalyst in

Figure 2A. Sequential implementation of the split reaction c « a + b with


subsequent separation of the products a and b.

In Fig. 2B, the simultaneous implementation of reaction


Figure 1B. Implementation of the process in Fig. 1A in a reactive distillation
and distillation is depicted. Substance c is fed into the column
column. C-1 where it is decomposed in the presence of a catalyst.

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Within the column, which is completely filled with catalyst, the into column C-2). This process, containing columns C-2, C-3
liquid phase is always in chemical equilibrium. Thus, the line of and C-4, is equivalent to the so-called generalized process for
chemical equilibrium, i.e., the reactive distillation line, the separation of azeotropic mixtures [3].
describes the internal concentration profile. At the top of
the column, pure substance a can be separated; at the bottom
of the column, pure substance b. It is worth noting that, due to
the chemical conversion, the two products D Ç and B
Ç do not lie
on a straight line through FÇ in the ternary diagram.

Figure 2B. Implementation of the process in Fig. 2A in a reactive distillation


column.

The process depicted in Fig. 2B is only possible when a


reactive azeotrope does not occur. The potential for this to
happen [s. 1] occurs when the reaction chemical equilibrium
state is close to the right-hand side of the triangle, as can be
seen in Fig. 2B. Figure 3A. Sequential implementation of the split reaction c « a + b and the
separation of the products ab in a system with two binary azeotropes.
The advantages of reactive distillation compared to
conventional distillation are especially large when the
In order to separate the reactor effluents into their pure
distillation process is hindered through the presence of
products a, b and c, it is necessary to place an adequate
reactive azeotropes. An excellent example of such a case is
entrainer e into the distillation column. Along with the
presented in Fig. 3A, where the following reaction is
addition of an entrainer, the separation is only possible when
considered:
the border distillation line for the mixture e-a-b is sufficiently
x x
c « a + b with KR = a b (3) curved.
xc
Fig. 3B presents the process for simultaneous implementa-
It is assumed that two nonreactive azeotropes with an tion of reaction and distillation in a single column. For an
intermediate distillation boundary occur (Fig. 3A, below left). appropriate value of the equilibrium constant KR, no reactive
Both products a and b must be separated into their pure forms. azeotrope occurs [1]; the reactive distillation line describing
For the sequential implementation of reaction and distilla- the concentration profile within the reaction zone runs from
tion (Fig. 3A), the equilibrium state R Ç 1 is reached in the
the intermediate boiler b towards the low boiler a. The column
reactor R-1. The ternary mixture is then fed into column C-1 is entirely filled with catalyst, as both desired products lie on
where the high boiler c is separated as the bottom fraction B Ç1
and is recycled back into the reactor. The distillate D1 is aÇ
binary mixture ab that contains a minimum azeotrope. This
mixture can be separated into its pure substances with the use
of a low boiling entrainer e. Therefore, the separation in
column C-2 yields pure substance a (bottom product B Ç 2) and a
binary azeotrope (distillate D Ç 2). By adding the entrainer e
(fraction D Ç 4), a mixture is obtained that lies in the left
distillation region of the mixture e-a-b (Fig. 3A, below right).
In this region, the high boiler b can be separated as bottom
fraction B Ç 3. The distillate fraction D Ç 3 lies in the concave
region of the distillation boundary and, hence, can be
separated within column C-4 into distillate fraction D Ç4
Figure 3B. Implementation of the process in Fig. 3A in a reactive distillation
Ç
(entrainer) and bottom fraction B4 (which is recycled back column.

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the reactive distillation line; a nonreactive section is not Figure 4B presents the process for simultaneous implemen-
necessary. Thus, reaction and distillation can be achieved in a tation of reaction and distillation. Both reactants are
single column. For reactions with large energy expenditures or separately fed into the reaction zone. It is important that the
consumption, it is appropriate to install an additional reactor low boiler a is fed at the lower end of the reaction zone and the
to perform the majority of the conversion. The superiority of high boiler b at the upper end of the column. In addition, a
reactive distillation compared to the conventional process is vapor feeding of the low boiler is advantageous. Thus, the
obvious when considering the process schemes in Figs. 3A and liquid phase contains a surplus of high boiler b, as the low
3B. boiler a is mainly present in the vapor phase. The small amount
of soluble low boiler in the liquid phase is converted into the
desired product c according to the main reaction (4A). Thus,
1.3 Main Reactions and Side Reactions
the main reaction is favored. As the reaction product c has a
higher boiling temperature than the reactants a and b, it is
For the simultaneous implementation of reaction and
continuously removed from the reaction zone from below.
distillation in a countercurrent column, the reaction products
High concentrations of c are only reached in the lower part of
are continuously removed from the reaction zone. For this
the column, where the low boiler a and catalyst are not
reason, complete conversion can almost be reached, even for
present. As a result, the side reaction (4B) does not occur.
reversible reactions. This removal of reaction products is very
Thus, even for reversible reactions, complete conversion can
effective for the suppression of undesired side reactions.
almost be reached and the side reaction can be successfully
The following reaction mechanism is considered:
suppressed.
xc
a + b « c with KR1 = (4A)
xa xb

xd
a + c « d with KR2 = (4B)
xa xc
Substance c and substance d are the desired and undesired
side products, respectively. For a fast reaction, a one-step
reactor always yields the reaction equilibrium of the complete
reaction, i.e., the product contains both substances b and c.
The process with sequential implementation of reaction and
distillation is depicted in Fig. 4A. It can be seen that two
distillation columns are necessary to separate the noncon-
verted reactants a and b and the undesired product d from the
reactor effluent.

Figure 4B. Implementation of the process in Fig. 4A in a reactive distillation


column. The undesired side reaction is efficiently suppressed if the low-boiling
reactant is fed into the reactive section of the column beneath the high-boiling
reactant.

1.4 Synthesis Reactions with Two Products

In general, it can be stated that reactive distillation is the


more advantageous the more components are present in the
Figure 4A. Conventional process for the implementation of the reaction a + b « process. This is to be shown using a quaternary mixture with
c and the undesired side reaction a + c « d. Two distillation columns are the following reaction mechanism:
necessary to separate the main product c in its pure form.

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xb xc
a + d « b + c with KR = (5A) absorption section between the two feed streams, a distillative
xa xd
rectifying section above the upper feed, and a distillative
Reactants a and d are the low and high boilers, respectively, stripping section beneath the lower feed. In the column core,
while b and c are the intermediate boilers. The equilibrium similar behavior to extractive distillation [5] occurs. In the
constant is greater than one, i.e., the reaction equilibrium lies absorption section, the internal concentration profile must
more to the product side. Fig. 5A presents the conventional differ from a distillation concentration profile, as there are
process of sequential reaction and distillation. The reactor multiple feeds which are contrary to the boiling sequence.
effluent contains all four components, with the intermediate Therefore, separation profiles occur that are beyond the
boilers having a surplus. In column C-1, a so-called preferred separation regions valid for distillation. Due to this fact, it is
separation [4] takes place with a distinct separation occurring possible for the reactive distillation products to lie on different
between a and d and a distribution of intermediate boilers b reactive distillation lines. An important condition for this
and c both in the distillate DÇ 1 and in the bottoms B Ç 1. Both process is that the reactant boiling temperatures are quite
fractions are separately fed into column C-2, in which pure different. Only then it can be guaranteed that the reactants
substance a is separated as the distillate and pure substance d will move countercurrently within the column.
as the bottom product. These two substances are the
nonconverted reactants and are therefore recycled back into
the reactor. The intermediate boilers b and c are removed
from column C-2 through a side-product stream. This fraction
is then fed into column C-3 where it is separated into pure
substance b (distillate) and pure substance c (bottom
product). In this case, three distillation columns are required
for the downstream processing of the quaternary mixture.

Figure 5B. Implementation of the process in Fig 5A in a reactive distillation


column. As the products c and d lie on different reactive distillation lines, a
multiple feeding of the reactants is necessary.

2 Industrial Processes of Reactive Distillation


Figure 5A. Sequential process for the implementation of the reaction a + d « c +
b. As the products occur in excess, the distillation is considered to be a preferred
separation. As explained above, the simultaneous implementation of
chemical reaction and distillation in a countercurrent column
Fig. 5B presents the process for simultaneous implementa- is a promising alternative to the conventional sequential
tion of reaction and distillation in a column. To achieve implementation of these two processes. The main advantages
complete conversion and complete separation, it is necessary of reactive distillation can be summarized as follows:
to feed the high boiler d, in its liquid state, into the upper part l Use of the exothermal heat of reaction for the distillation
of the column and the low boiler a, in its vapor state, into the process;
lower part of the column. This is typical for absorption l Achievement of higher yields for reversible reactions;
columns. The low boiler a, moving upwards within the column l Simplification of reactor effluent separation;
together with the vapor phase, is selectively absorbed by the l Ability to overcome distillation boundaries, e.g., azeo-
high boiler d and chemically converted into the products b and tropes, border distillation lines or border distillation planes.
c. The heavy product c remains in the liquid phase and, thus, These synergetic effects are of increasing importance in
moves downwards within the column; the light product b is industry. In literature, a great number of chemical syntheses
vaporized and moves upwards. At the top of the column, pure are described in which it could be advantageous to utilize the
distillation separates components b and d, while at the bottom reactive distillation technology. Table 1 contains a summary of
of the column, pure distillation separates components a and c. some of these systems, with the following paragraphs
Thus, the entire column consists of three sections: an presenting some industrially important processes.

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Table 1. Selected systems for reactive distillation modified from [14±16]. addition, MTBE and methanol form a minimum azeotrope,
and a further minimum azeotrope exists between methanol
and n-butane. Due to the existence of these three minimum
azeotropes, a border distillation plane exists in the quaternary
mixture, which forms a barrier against distillation. As a result,
a sequential implementation of reaction and distillation is
difficult.

Figure 6A. Properties of the system for MTBE-synthesis.

Much more advantageous is the reactive distillation


technology. Fig. 6B shows the qualitative path of the reactive
distillation lines, which lie on the conditions for chemical
equilibrium that form a cone mantle. All reactive distillation
lines start at the methanol vertex and end either at the
isobutene vertex, which has the lowest boiling temperature, or
at the n-butane/methanol azeotrope. A so-called reactive
border distillation line occurs, separating the regions with
different end points of reactive distillation lines.
2.1 Synthesis of MTBE

Methyl tertiary-butyl ether (MTBE, C5H12O) is an effective


antiknock substance for motor fuels, with a production of
20.106 tons per year [6]. MTBE is mainly synthesized from
isobutene (C4H8) and methanol (CH3OH) in the presence of
either a homogeneous catalyst (e.g., H2SO4) or a hetero-
geneous catalyst (e.g., acid ion-exchange resins). The follow-
ing reaction mechanism occurs:

C4H8 + CH3OH « C5H12O (5B)

In general, the original mixture additionally contains a high


concentration of n-butane, which behaves as an inert for this
reaction. Data of the reaction technique is well known [e.g.,
7,8].
Fig. 6A presents the most important characteristics of the
mixture. For high concentrations of isobutene, the reactants Figure 6B. Course of reactive distillation lines in the MTBE-system. The fat line
isobutene and methanol form a minimum azeotrope. In starting at the MTBE represents the internal concentration profile.

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In order that the distillate can condensate by cooling water,


the column must operate at a pressure of 8 bar. The column
contains 14 trays, with the top 8 trays being filled with catalyst
[9]. In this column, complete conversion of isobutene is almost
achieved. The minimum azeotrope between n-butane and
methanol is removed as distillate product, and the bottom
fraction is pure MTBE representing the high boiler in the
mixture. Fig. 6B qualitatively presents the concentration
profile within the column. Above the feed location, the profile
follows a reactive distillation line, beneath the feed location,
the profile follows a nonreactive distillation line leading to the
high boiler MTBE.
Due to the chemical reaction, the mass balance around the
column is not a straight line within the tetrahedron (see
Fig. 6B). A projection along the corresponding stoichiometric
line of the bottom product into the n-butane/isobutene/
methanol plane yields a straight line that contains the feed FÇ
and both product fractions D Ç and BÇ ¢.

Figure 7. Synthesis of ethylene glycol in a reactive distillation column.

2.2 Synthesis of Monoethylene Glycol


2.3 Synthesis of TAME

The authors [10] investigated the suppression of a side As there is an insufficient amount of isobutene for the
reaction in the synthesis of monoethylene glycol (C2H6O2) synthesis of MTBE, tertiary amyl methyl ether (TAME) is
from ethylene oxide (C2H4O) and water (H2O). The following increasingly applied as an antiknock substance for motor [11].
main reaction occurs The advantage of TAME is that it is produced from a C5-
alkane cut.
C2H4O + H2O « C2H6O2 (6A)
A modern process for the synthesis of TAME is presented in
Fig. 8 [11]. The C5-cut contains about 15±20 mole-% isoamyl,
As undesired side product, diethylene glycol is formed
which is converted together with methanol into TAME. In the
according to the following mechanism:
first process step, impurities that poison the catalyst are
C2H4O + C2H6O2 « C4H10O3 (6B) removed by using a water scrubber. The main portion of the
reaction (about 70%) takes place in a reactor with a fixed-bed
The boiling temperature of the four participating sub- catalyst (sulfuric ion-exchange resin). Complete conversion is
stances increases from the low boiler ethylene oxide (a) over established in a reactive distillation column where the high
water (b) and ethylene glycol (c) to diethylene glycol (d). The boiler TAME is removed as the bottom product. The distillate,
reaction is sufficiently fast, even in the absence of a catalyst. an azeotropic mixture consisting of C5-olefines and methanol,
Fig. 7 presents the process in a single column with 10 is fed into an extractor where methanol is extracted by using
equilibrium trays. It is important that the reactants are water. The methanol/water stream is separated by means of
separately fed into the column, with the lower-boiling distillation, with both fractions then being recycled within the
ethylene oxide approximately fed into the middle of the process.
column and the high-boiling water fed into the top of the
column. The above authors found through rigorous simulation
that, despite stoichiometric feeds into the column, the amount
of water in the liquid phase is approximately 200 times higher
than the amount of ethylene oxide. Ethylene oxide is mainly
present in the vapor phase, thus, the main reaction (6A) is
strongly favored. The amount of ethylene glycol throughout
the upper part of the column is smaller than 5%. In the lower
part of the column, with four equilibrium trays, a concentra-
tion of 95% ethylene glycol is reached; the other 5% being
mainly diethylene glycol and nonconverted water. According
to the above authors, an excess of 60% water would be
necessary to achieve the same selectivity in a plug flow reactor
The excess water would then have to be subsequently
separated from the product. Figure 8. Process for the synthesis of TAME.

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The physical and chemical properties of the system are entrainer, azeotropic distillation and extraction using ethyl
described in detail in [11]. A methanol/C5-olefine azeotrope acetate.
and a methanol/TAME azeotrope exist along with an As the chemical reaction is limited through equilibrium, the
intermediate border distillation line. In the reactive section, implementation of the process in a reactive distillation column
the reactive distillation column is filled with an unstructured is in principle possible. Fig. 9A presents the equilibrium plane
catalytic packing, while the nonreactive sections simply within the quaternary mixture methyl acetate/methanol/
contain a conventional unstructured packing. water/acetic acid for an equilibrium constant Kx = 5.2. The
products methyl acetate and water both lie on the chemical
equilibrium plane and thus, in principle, can be separated by
2.4 Synthesis of Methyl Acetate reactive distillation into their pure components. Due to the
minimum azeotrope between methyl acetate and methanol,
Methyl acetate is a common component in many varnishes both products are inflexion points of reactive distillation lines.
and adhesives due to its excellent solvent properties. It is Therefore, the products do not lie within the separation
produced by a methanol and acetic acid esterification process regions and, hence, the column must contain a chemical
together with water as side product. The equilibrium constant absorption section (see chapter 1.4).
Kx is independent of temperature and has a constant value of Fig. 9B presents the process with simultaneous implemen-
5.2 [12]. The phase equilibrium of this quaternary mixture tation of reaction and distillation according to [12]. The
exhibits a minimum azeotrope between methyl acetate and column includes four different sections that are defined by the
water and a minimum azeotrope between methyl acetate and feed locations. The reactive part is between the catalyst feed
methanol, resulting in an intermediate border distillation line (H2SO4) and the low boiler methanol feed, which enters the
(Fig. 9A). In addition, for large amounts of water, a tangential column only slightly above the bottom. Due to the high
pinch point exists between acetic acid and water, severely temperatures which exist in this part, the methanol is quickly
deteriorating the separation of the reactor effluents. vaporized and begins moving upwards. In the presence of the
catalyst, the methanol is selectively absorbed by the acetic
acid and converted into methyl acetate and water. The water
remains in the liquid phase and moves downwards, while the
methyl acetate, the lowest boiling component, is vaporized
and moves upwards.
In the section above the reactive part, a physical absorption
of methanol in acetic acid takes place as in extractive
distillation. Above this extractive section, a distillative
separation between methyl acetate and acetic acid occurs
that requires very few stages and a minimal reflux ratio. At the
bottom of the column, a simple distillative separation between

Figure 9A. Equilibrium plane and reactive distillation lines in the mixture
methyl acetate/methanol/water/acetic acid.

Literature [9,12] states that a process for the synthesis of


methyl acetate (the so-called Eastman-Kodak-process), ap-
plied until the eighties, consisted of a reactor and nine
columns. Along with several distillation steps, the process Figure 9B. Simultaneous implementation of the methyl acetate synthesis in a
included extractive distillation using ethylene glycol as an reactive distillation column.

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water and methanol takes place, which is additionally [3] Stichlmair, J.; Herguijuela, J. R., Separation Regions and Processes of
Zeotropic and Azeotropic Ternary Distillation, AIChE J. 38 (1992) 10,
simplified through the presence of the sulfuric acid. pp. 1523±1535.
In comparison to the conventional process, reactive [4] Stichlmair, J., Zerlegung von Dreistoffgemischen durch Rektifikation,
distillation greatly reduces implementation costs. The re- Chem. Ing. Tech. 60 (1988) 10, pp. 747±754.
[5] Bauer, M. H.; Stichlmair, J., Synthesis and Optimization of Distillation
quired equipment is reduced from one reactor and nine Sequences for the Separation of Azeotropic Mixtures, Comp. Chem. Eng.
columns to a single reactive distillation column with a 19 (1995) Suppl., pp. 15±20.
[6] Rehfinger, A.; Hoffmann, U., Kinetics of Methyl Butyl Ether Liquid
subsequent vaporizer. For the use of catalytic packing, i.e., a
Phase Synthesis Catalysed by Ion-Exchange Resin, Chem. Eng. Sci. 45
heterogeneous fixed catalyst, the subsequent vaporizer can (1990) pp. 1605±1617.
also be neglected [13]. [7] Espinosa, J.; Aguirre, P.; Perez, G., The Product Composition Regions of
Single-Feed Reactive Distillation Columns, Ind. Eng. Chem. Res. 34
Received: June 19, 1998 [B 6002] (1995) pp. 853±861.
[8] Thiel, Ch.; Sundmacher, K.; Hoffmann, U., Residue Curve Maps for
Heterogeneously Catalysed Reactive Distillation of Fuel Ethers MTBE
and TAME, Chem. Eng. Sci. 52 (1997A) 6, pp. 993±1005.
[9] Beûling, B.; Schembecker, G.; Simmrock, K. H., Design of Processes with
Symbols used Reactive Destillation Line Diagrams, Ind. Eng. Chem. Res. 36 (1997) 8,
pp. 3032±3042.
[10] Ciric, A. R.; Gu, D., Synthesis of Nonequilibrium Reactive Distillation
a [±] low boiler Processes by MINLP Optimization, AIChE Journal 40 (1994) 9, pp. 1479±
b [±] intermediate boiler 1487.
Ç
B [kmol/s] bottom product [11] Hoffmann, U.; Krummradt, H.; Rapmund, P.; Sundmacher, K., Erzeugung
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