Chemical Engineering Science 58 (2003) 809 – 814

www.elsevier.com/locate/ces

A general approach for the conceptual design of counter-current reactive

separations
Hans J. Gorissen∗
Akzo Nobel Chemicals bv, P.O. Box 9300, NL-6800 SB Arnhem, The Netherlands

Abstract

This paper is on a number of general aspects in the preliminary design of reactive separations. It provides a method for easy identi-cation
of reaction processes that can be improved by application of reactive separation. The method is based on analyzing chemical reactions
by making a distinction between intensive and extensive concentration requirements for the involved chemical substances. Con2icting
concentration requirements are indicators for a potentially attractive application of reactive separation. Here, the focus is mainly on
improving the performance of the reaction process.
Guidelines are given for the selection of a suitable separation technology on the basis of the intensive and extensive concentration
assessment, together with a checklist on various practical issues. Further, a method for conceptual process design of a multi-stage
counter-current reactive separation process is given, which is guided by the extraction factors of all relevant reaction ingredients. Thus,
the technical feasibility of such a reactive separation process can be assessed in an early stage of the development. The resulting process
concept is a good starting point for more detailed process development work.
? 2003 Published by Elsevier Science Ltd.

Keywords: Chemical reactors; Reactive separations; Mass transfer; Multiphase reactors; Reaction engineering; Process synthesis

1. Introduction • The development of a reactive separation process is ex-

Although there is general agreement that integration of
reaction and separation is a very useful and powerful tool
in chemical reaction engineering, the present number of in-
dustrial applications is still relatively low. There are many
possible reasons for the limited number of applications of
reactive separations: unawareness of the potential, the eco-
nomic risk, the di;culty of the technology, the limited com-
mercial availability of equipment, restrictions regarding the
required plant 2exibility, etc. Especially, industrial applica-
tions of continuous counter-current reactive separations are
still rare. The main reasons for this are the following:
• Despite the signi-cant potential of this technology, it is
often di;cult to identify chemical processes that have an
apparent need for improvement by reactive separation.
• It is di;cult to develop and design continuous counter-
current reactive separations because of their complex na-
ture and the larger amount of kinetic data and physical
parameters that are required.
∗ Tel.: +31-263662697; fax: +31-263665871.
E-mail address: hans.gorissen@akzonobel.com (H.J. Gorissen).
pensive and risky: After years of work, a concept may
appear not to be feasible.
However, the high potential of reactive separations and the
continuous progress in the development of new separation
and reaction technologies will result in increased use of this
technology.
This work is on a general, conceptual approach for in-
vention and development of reactive separation processes.
It focuses mainly on the initial phases of the design of such
processes (invention and process synthesis), not on the de-
tailed design and modeling. The following questions are ad-
dressed in this work:
• Which are the indicators that show easily whether a pro-
cess has a need for reactive separation? Such indicators
guide researchers and engineers in systematical invention
and identi-cation of new potential reactive separation pro-
cesses.
• How to make a conceptual design of a continuous
counter-current reactive separation process?
• How to check the technical feasibility of a potential reac-
tive separation process in an early stage of the develop-
ment?

0009-2509/03/$ - see front matter ? 2003 Published by Elsevier Science Ltd.

doi:10.1016/S0009-2509(02)00611-5
810 H.J. Gorissen / Chemical Engineering Science 58 (2003) 809 – 814
The general focus is on improving the chemical reaction.
Here, the term reactive separation does not only apply to the
integrated removal of products from a chemical reactor. An
integrated separation process can also be used to control the
supply of highly reactive reagents to a reaction system.
2. The concept of intensive and extensive concentrations
An indicator for “the reaction’s needs for reactive separa-
tion” on the basis of con2icting concentration requirements
follows from making a distinction between the extensive
and intensive aspects of reagent and product concentrations.
The extensive aspect determines only the quantity of a com-
ponent, whereas the intensive concentration determines its
activity and reactivity. The intensive concentration refers to
the actual concentration in mol=m3 in a homogeneous phase
that is normally used in kinetic relations, equations of state,
etc. For the extensive concentration diGerent de-nitions can
be used, depending on the researchers’ intention, as will be
shown in the process examples in Section 3. Any de-nition
of the extensive concentration will be based on a quantity
of a component.
An example of these de-nitions can be demonstrated on
the basis of the following reaction system:
Main reaction:
A + B → C; R1 = k1 CA CB : (2.1)
Unwanted parallel reaction:
2A → U; R2 = k2 CA2 : (2.2)
In these relations CA and CB represent the intensive concen-
trations of both reagents. R1 and R2 are the reaction rates.
For selectivity reasons, R1 =R2 must be maximized, so the
intensive concentration ratio CB =CA must be increased as
much as possible. At the same time the reaction stoichiom-
etry calls for equal amounts of A and B, so the extensive
concentration ratio must be 1. Here, we have an example of
a con2icting concentration requirement: extensively, equal
concentrations of A and B are preferred, whereas intensively
the concentration of A must be amply lower than the con-
centration of B.
One way to meet such con2icting requirements is to add
a second physical phase to the reactor, which extracts more
A than B (mA ¿ mB ). This can be any phase that does not
mix with the reaction phase, e.g.: a gas (when the reaction
phase is not a gas), a liquid, the surface of a solid adsorbent,
etc. The reaction should only occur in the reaction phase,
for example, because of the presence of a catalyst only in
the reaction phase or because there is no B present in the
extraction phase.
Let us de-ne the extensive concentration, Cext: , on the
basis of the total quantity of a reagent in both phases per
volume of the reaction phase. At phase equilibrium for
component A we -nd
C A V R + m A C A VE
Cext:; A = = CA (1 + A )
VR
m A VE
with A = ; (2.3)
VR
where A is the extraction factor of component A. It is the
ratio of the respective quantities in the extraction phase and
the reaction phase. With this de-nition of the extensive con-
centration, the following general relation between intensive
and extensive concentration holds for any component in a
two-phase system at physical equilibrium:
Cextensive
Cintensive = : (2.4)
1+
Suppose that stoichiometric amounts of A and B are fed to a
batch reactor, so Cext:A =Cext:B . Suppose further that we have
a suitable extraction phase with mA ¿ mB , so A ¿ B . In
case of phase equilibrium, the intensive concentration ratio
of A and B follows from
CB Cext:B =(1 + B ) 1 + A
= = ¿ 1: (2.5)
CA Cext:A =(1 + A ) 1 + B
This relation shows how addition of a suitable extraction
phase can be used to improve the selectivity by increasing
the intensive CB =CA , while maintaining stoichiometric quan-
tities of A and B by keeping equal extensive concentrations.
The larger the diGerence between A and B the larger the
eGect.
So far, it was assumed that the system is at phase equi-
librium. When the mass transfer is slow compared to the
reaction rate, it can be considered to feed the reagent B via
the reaction phase and reagent A via the extraction phase.
Then, due to the mass transfer limitation, CA will be even
lower than according to relation 2.4. Thus, it can be seen
that a mass transfer limitation can give an extra contribution
to the selectivity enhancement.
It should be noted that in this example the integrated sep-
aration improves selectivity of the reaction, but also reduces
the overall reaction rate. The following section shows more
practical examples of reaction systems with con2icting con-
centration requirements.
3. Process examples
3.1. General
Con2icting requirements for the intensive and extensive
aspects of a concentration point to an evident need for reac-
tive separation. Such con2icting requirements are found by
a systematic analysis of the reaction scheme. The following
situations indicate a potential concentration con2ict:
• Equilibrium reaction.
• Parallel reactions: a component in the reaction scheme
can participate in diGerent chemical reactions.
 H.J. Gorissen / Chemical Engineering Science 58 (2003) 809 – 814
Table 1
Concentration requirements for equilibrium reaction A + B ↔ C + D
Concentration type Requirements
Intensive High A; B; low C; D
Extensive, reactor contents Low A; B; high C; D
Extensive, total feed intake Equal A and B
• Consecutive reactions: a chain of similar consecutive re-
actions giving an extensive series of homologous prod-
ucts from only two raw materials.
• Catalytic cycle.
• Reaction with a dangerous or harmful component.
These situations will be explained on the basis of examples.
3.2. Equilibrium reaction
Equilibrium reactions are quiet common in chemical
processes, for example in esteri-cation, trans-esteri-cation,
amidation, hydrolysis of oils, etc. Because of the reaction
equilibrium, the extent of the conversion is limited in case
of a homogeneous reaction system without integrated sepa-
ration. The general approach for obtaining high conversion
is the removal of one of the products from the reaction sys-
tem. This can be done either inside the reactor or after the
reactor, with a recycle of the unconverted reagents back to
the reactor. A common example is the integrated removal
of water from an esteri-cation reaction mixture by simply
boiling it oG during the reaction.
The need for reactive separation follows from con2icting
requirements for the intensive and extensive product con-
centrations, as can be seen in Table 1. Intensively, low prod-
uct concentrations are required, because a high intensive
product concentration pushes the reaction equilibrium back
to the raw materials. The extensive product concentrations
should be high, because preferably all raw materials should
be completely converted to products.
3.3. Parallel reactions
The in2uence of reagent concentrations in case of parallel
reactions is already worked out in the example in Section 2.
Of course, primarily, the reaction conditions (temperature
and pressure) and catalyst choice should be optimized. Next,
optimization of the reagent concentrations must be consid-
ered. When one of the reactions is an equilibrium reaction,
the product concentrations of this reaction can also be used
to guide the reaction. If for example, the unwanted reaction
is an equilibrium reaction, then
Unwanted parallel reaction:
2A ↔ U; R2 = k2 CA2 − k−2 CU : (3.1)
Here, a high intensive concentration of U is favorable, al-
though the extensive concentration of U must be low (low
811
Purpose
Equilibrium at high conversion of A and B
High conversion of A and B
Reaction stoichiometry
production of U allowed). Table 2 shows that there is a
number of con2icting concentration requirements in this
system.
When the main reaction is an equilibrium reaction, a low
intensive concentration of product C is required for high and
fast conversion, whereas the extensive concentration of the
preferred product C must be high.
There are numerous examples of reactions with unwanted
parallel reactions. For example, reactions of types 2.1 and
2.2 occur in the acid catalyzed alkylation of an alkene (com-
ponent A) with an alkane (component B).
3.4. Consecutive reactions, homologous product series
In case of one reagent with multiple identical functional
groups, a mixture of a number of similar reaction products is
obtained (mixture of homologs). This occurs, for example,
in production of esters of polyoles like pentaerythritol and
glycerol, in several chlorination processes, in nitri-cation of
toluene, and in many other reactions. Especially, when the
required product component should contain some unreacted
functional groups, it is generally not possible to obtain a
single component with 100% selectivity.
When both reagents each have more than one functional
group, the situation is much more complex. The number
of diGerent reactions as well as the number of homologous
products is in fact in-nite. With a feed composition close
to stoichiometry polymers can be produced. The situation
is explained in Fig. 1 on the basis of an example reaction:
Friedel Crafts alkylation of chloroform and benzene. Here,
both reagents have at least three functional groups and all re-
action steps are equilibrium reactions with the highly volatile
HCl as byproduct. The substituted benzene is more reactive
than benzene. Thus, a large excess of benzene is required
to obtain mainly products on the left side of the reaction
scheme.
In this kind of reaction system the preferred products
should combine a low intensive concentration (low ten-
dency for further reaction) with a high yield (high exten-
sive concentration). Here, the main con2icting concentra-
tion requirement is the high intensive benzene chloroform
ratio with the extensive preference of stoichiometric feed
ratio. In practice, the benzene excess is used as reaction
solvent. Theoretically, polymer formation or formation of
highly substituted compounds can be avoided by limiting
the degree of conversion by operation at high HCl concen-
tration (high-pressure reaction).
812 H.J. Gorissen / Chemical Engineering Science 58 (2003) 809 – 814

Table 2
Concentration requirements for parallel reactions according to Eqs. (2.1) and (3.1)

Concentration type Requirements Purpose

Intensive High B=A ratio, high U Selectivity

Intensive High A and B Higher reaction rate
Extensive, reactor contents Low A; B; U ; high C High conversion and selectivity
Extensive, total intake Equal A and B Reaction stoichiometry

AlCl3 CHCl2
+ CHCl3 + HCl

CHCl3
AlCl3 HCl HCl AlCl3

CHCl CHCl2

CHCl2

CHCl3
AlCl3 HCl etc... HCl AlCl3

HCl2C CHCl2
CH
CHCl2

in case of very polymers in case of in case of

large benzene excess stochiometricmix chloroform excess

Fig. 1. Reaction scheme of Friedel Crafts alkylation of two multi-functional reagents.

A allel reactions. Some steps may be equilibrium reactions.

Int. 2 Control of the catalyst intermediate states can contribute to
Int. 1
improved conversion and selectivity. The reaction rate con-
stants per step and the concentrations of the reagents de-
A termine the steady-state distribution of the diGerent cata-
Int. 3
Product C lyst states. Thus, the concentration ratio of the raw mate-
B By-product U rials can be used to control the overall reaction rate and
selectivity. There are numerous examples for this type of
Fig. 2. Example of a catalytic cycle. reactions.

3.6. Reaction with dangerous or harmful components

Similar situations occur in the production of polyesters,
ethylene amines, in alkene/alkane alkylation, etc.
3.5. Catalytic cycle
Generally, the mechanism of catalytic reactions is of the
form that is presented in Fig. 2. During the reaction, the
catalyst is present in all of the intermediate states (here:
Int.1, Int.2 and Int.3). The scheme in Fig. 2 can explain a
catalytic mechanism for reactions 2.1 and 2.2.
Such a catalytic cycle can be seen as a series of consec-
utive reactions. By-product formations can be seen as par-
In reactions with dangerous or harmful components, the
risk can be reduced by allowing only a low hold-up of
the risk causing components (low extensive concentration).
This can be achieved by feeding these components at a suf-
-ciently low feed rate, compared to the reaction rate. Prefer-
ably, the risky components should be very reactive (high in-
tensive concentration), to prevent possible build-up. Process
examples can be found in various processes, with reagents
like: phosgene, HCN, chlorine, ammonia, sodium, ethylene
oxide, O2 (in partial oxidation close to explosion region),
etc.
 H.J. Gorissen / Chemical Engineering Science 58 (2003) 809 – 814
4. Selection of a separation method
Up to this point, this paper is aimed at identifying the
needs of a reaction for an integrated separation. These needs
are identi-ed without considering the actual availability of
a suitable separation process. So, the next step is to discover
separation methods that can be used to improve the perfor-
mance of the reaction. I.e., to select a separation that copes
with the con2icting concentration requirements of the reac-
tion system. This step is similar to the selection of separa-
tion methods in general, although there are some additional
requirements and considerations. Generally, the choice of
the separation process is largely determined by the type of
reaction phase and the choice of the extraction phase.
In the selection of a the separation technology, the fol-
lowing primary checks should be made:
• Does the separation remove the right component(s)
from the reaction phase (does the selected separation
method actually avert the con2icting concentration re-
quirements)?
• Are the reaction conditions (T; p and composition) com-
patible with the separation conditions?
• Does the extraction phase itself act as inert (or at least
harmless) for the reaction? How does this separation aGect
the other components in the reaction mixture?
• Can reactions also occur in the extraction phase and what
are the consequences of that?
• Are there other practical aspects that aGect the feasibility
of the process (like formation of solids, fouling, foaming,
excessive heat formation, etc.)?
The selection of a suitable separation method may be an
iterative process. When the selected method does not pass
the primary checks (or when it fails in a later stage), an
alternative separation should be selected.
5. Conceptual process design based on the extraction
factor
In the next step, of the development choices have to be
made on the type of process, i.e., batch or continuous and
single stage or multi stage. For a multi stage continuous
there is a choice between co-current and counter current. The
complexity of the process development and design depends
very much on these choices. In general, a counter-current
continuous reactive separation process is most complex.
The process design phase starts with the conceptual pro-
cess design (process synthesis). This is in fact the prepara-
tion of a -rst sketch, which shows how the feed and prod-
uct streams are connected to the reactive separator and ex-
plains how the process works. In this section, a method for
the process synthesis of continuous counter-current reactive
separations is discussed, which is based on the extraction
factors of the reagents and the products. In a continuous
813
Extraction phase,
Feed position of A
FE
Counter current separation process
Reaction phase,
Concentration of A in
FR
the reaction phase
εA > 1
Place
Concentration of A in
the reaction phase
εA ≈ 1
Place
Concentration of A in
the reaction phase
εA < 1
Place
Fig. 3. Typical concentration pro-les in continuous multi-stage
counter-current separators.
process a diGerent de-nition for extraction factor is used.
Here, the extraction factor is based on 2ow rates instead of
quantities of the physical phases (as was done in Eq. (2.3).
Now:
m A FE
A = : (5.1)
FR
In a multi-stage counter-current process the extraction fac-
tor determines the ratio of the transport capacities of ex-
traction and reaction phase. Consequently,  also determines
the dominant direction of transport. This aGects the concen-
tration pro-les of the reagents in a counter-current reactive
separation process. Fig. 3 shows the concentration pro-les
in a counter-current separator with a central feed position of
component A, without chemical reaction.
When A ¿ 1, component A is mainly transported with the
extraction phase. For A ¡ 1, component A is mainly trans-
ported with the reaction phase. In case of A ≈ 1, component
A has a tendency to accumulate near the feed location, which
is preferable for a homogeneous catalyst. The extraction fac-
tors can be manipulated by variation of the 2ow rate of the
extraction phase, FE . The extraction factors of all compo-
nents increase with increasing FE . This knowledge can be
used in the conceptual design of reactive separations.
As an example, the concentration pro-les have been stud-
ied theoretically for a reactive separation with reactions 2.1
and 2.2, where the reaction selectivity asks for su;ciently
high CB =CA in the reaction phase. It is assumed that the mass
transfer rate is su;ciently fast compared to the rate of re-
action and that mA ≈ 10 mB . Depending on the quantity of
814 H.J. Gorissen / Chemical Engineering Science 58 (2003) 809 – 814

Extraction phase
A and B preferential directions of transport. Thus, they must be fed
Counter-current reactive separator
at diGerent positions, in order to let them move towards
Reaction phase each other. Now, there is a small region with CB =CA ¡ 1.
the reaction phase

This process has better selectivity than a reaction system

Concentrations in

B
without extraction phase but it is often less selective than a
εA > εB > 1 co-current operated reactive separator.
At lower 2ow rate of the extraction phase 1 ¿ A ¿ B
A
holds. Here, the reagents must be fed close enough to the
Place inlet of the reaction phase. Now, it appears in the lowest
pro-le in Fig. 4 that for the whole reaction phase CB =CA ¡ 1
Extraction phase
A B (although mA ¿ mB ). This can be explained by the fact that
A is closer to 1, resulting in more accumulation of A in the
Counter-current reactive separator
counter-current process. Consequently, this process has even
Reaction phase
the reaction phase

worse selectivity than a reaction system without extraction

Concentrations in

phase. Such a process makes no sense.

B
εA > 1 > εB This study shows how the concentrations of reagents can
be manipulated in a multi-stage counter-current reactive sep-
A aration process. In a similar way also the concentrations of
Place
products and intermediates can be in2uenced.

A and B
Extraction phase 6. Concluding remarks
Counter-current reactive separator
Reaction phase This work addresses a number of aspects of the invention
the reaction phase
Concentrations in

and preliminary design of reactive separation processes. It is

A aimed at passing the -rst development stages systematically
1 > ε A > εB
and it results in a starting point for further development and
B
more detailed modeling.
The work shows how opportunities for reactive separa-
Place tions can be identi-ed on the basis of the concept of inten-
sive and extensive concentrations. Further it helps in select-
Fig. 4. Concentration pro-les of reagents in a counter-current reactive
separation process. ing the most suitable separation technology on the basis of
a checklist. A method is given for the conceptual design of
a counter-current process.
extraction phase, three diGerent situations can be distin-
guished for counter-current systems, as is shown in Fig. 4.
At a su;ciently high 2ow rate of the extraction phase Notation
A ¿ B ¿ 1 holds. Then, the reagents have a tendency to
transport in the direction of the extraction phase. Thus, they C reagent or product concentration
must be fed close enough to the inlet of the extraction FE 2ow rate of the extraction phase
phase. There are two positive contributions to the high av- FR 2ow rate of the reaction phase
erage CB =CA of this process: The extraction phase absorbs k reaction rate constant
A better than B and the extraction factor of B is closer to kL a product of overall mass transfer coe;cient and spe-
1, so B accumulates more than A. The consequence is that ci-c interfacial area
this process has better selectivity than a co-current operated m partition coe;cient (extraction phase/reaction
reactive separator or a reaction system without extraction phase)
phase. R reaction rate
The other two situations in Fig. 4 are less attractive. VE volume of the extraction phase
At a moderately lower 2ow rate of the extraction phase VR volume of the reaction phase
A ¿ 1 ¿ B holds. Then, the reagents have diGerent  extraction factor