Ind. Eng. Chem. Res.

2006, 45, 2707-2714 2707

Comparison of Reactive Distillation with Process Alternatives for the Isobutene

Dimerization Reaction
Ravindra S. Kamath,†,§ Zhiwen Qi,† Kai Sundmacher,*,†,‡ Preeti Aghalayam,§ and
Sanjay M. Mahajani§
Max-Planck-Institute for Dynamics of Complex Technical Systems, Sandtorstrasse 1, D-39106 Magdeburg,
Germany, Process Systems Engineering, Otto-Von-Guericke-UniVersity Magdeburg, UniVersitätsplatz 2,
D-39106 Magdeburg, Germany, and Department of Chemical Engineering, Indian Institute of Technology
Bombay, Powai, 400076 Mumbai, India

Reactive distillation is an attractive alternative to conventional multiunit structures. In the case of irreversible
reactions involving several products, reactive distillation may effectively improve the selectivity toward a
desired intermediate product. However, multiunit processes for such reactions cannot be simply discounted
without a systematic comparison with reactive distillation. This work emphasizes such a comparison using
the isobutene dimerization reaction as an example. The multiunit configurations considered include the
conventional reaction-separation network with and without recycle and a distillation column coupled with a
side reactor. Potential configurations of process alternatives are generated for a wide range of the conversion
of isobutene and the alternatives are compared on the basis of the selectivity toward diisobutene achieved
and cost incurred for identical isobutene conversion. Results show that, for a given isobutene conversion, the
reactive distillation process is capable of providing the maximum selectivity among all the investigated
alternatives. However, the conventional processes are competitive when costing is also involved in the
evaluation.

Introduction control, even in the absence of a polar component. These results

strengthen the selection of the RD process for the dimerization
Alkylates are considered to be potential alternatives to MTBE, reaction.
whose status as a gasoline additive is questionable considering
Though RD seems suitable for the dimerization of isobutene
its association with groundwater contamination. One of the
from the technical point of view, practical issues, e.g., compli-
sources of alkylates is the dimerization of isobutene (IB) to
cated designs of the column internals and inconvenience in
diisobutene (DIB; i.e., isooctene) followed by hydrogenation.
catalyst handling during installation, removal, and regeneration,
There were claims that this indirect alkylation process is capable
suggest that external reactors might be favorable because of
of utilizing the existing facilities with reasonable revamping and
their flexibility. However, external reactors do not possess the
the feedstock used for MTBE production.1-3
separation effect in the reactive zone, which may hamper the
The dimerization reaction is a typical series-parallel reaction
product selectivity. To overcome the problems of RD and to
network with the desired product being an intermediate in the
somewhat maintain the benefits of the combined process,
network that ends with the undesired oligomers. Thus, both the
application of the side-reactor concept6,7 or reactive-pump
conversion of the reactant (IB) and the selectivity toward the
concept8 are suggested. This concept involves taking out a
desired product (DIB) are desirable to be maximized simulta-
stream from the distillation column at a strategic location and
neously. However, in many of such reactions, the conversion
introducing it into an external reactor or a series of reactors. In
and selectivity show an inverse relationship, i.e., as conversion
a sense, the reactor is coupled to the column but retains all the
increases selectivity decreases and vice versa. Since the reaction
characteristics of an external reactor with reaction conditions
is fast and highly exothermic,4 temperature control by external
very less limited by the distillation conditions. So far, systematic
cooling and addition of polar components have been traditionally
comparison of RD with other competitive processes is missing
used to improve the DIB selectivity. The reaction characteristics
in the literature; the only notable exception worth mentioning
make it an interesting candidate for reactive distillation (RD).
is the recent work by Kaymak and Luyben9 which demonstrates
RD can maintain a low concentration of the dimer in the reactive
this comparison for a hypothetical reversible reaction with ideal
zone by simultaneous distillation due to the difference of
vapor-liquid equilibrium (VLE).
component boiling points, thereby suppressing the further
oligomer-producing reactions. In our previous work,5 the For reactions such as dimerization, the final optimum
feasibility of the dimerization reaction in reactive distillation combination of values for the IB conversion and DIB selectivity
has been illustrated. Results showed that a RD column structure cannot be specified without doing a very rigorous optimization
similar to that commonly used for MTBE production can be analysis involving process cost. At a preliminary stage to select
successfully applied for the dimerization reaction and that high a process alternative, one can expect that the desired operating
selectivity to DIB can be obtained with adequate temperature point could lie anywhere within a wide window of the IB
conversion or DIB selectivity. Hence, the comparison needs to
be done bearing this fact in mind. The matter is complicated
* Corresponding author. Tel.: +49-391-6110351. Fax: +49-391-
6110353. E-mail: sundmacher@mpi-magdeburg.mpg.de.
by the fact that RD can involve nonlinear behavior, such as
†
Max-Planck-Institute for Dynamics of Complex Technical Systems. multiple steady states, which can significantly influence or
‡
Otto-von-Guericke-University Magdeburg. perhaps even tilt the balance in the favor of multiunit configura-
§ tions if RD is not operated in the optimal window. Hence, this
Indian Institute of Technology Bombay.

10.1021/ie051103z CCC: $33.50 © 2006 American Chemical Society

Published on Web 03/11/2006
2708 Ind. Eng. Chem. Res., Vol. 45, No. 8, 2006

Table 1. Configuration of the Base Case for the Reactive Distillation Process
total stages 30 total catalyst loading (kg) 700.64
reactive stages 4-26 C4 feed flowrate 100.0
pressure (MPa) 1.5 C4 feed composition (IB/nB, mol) 1.5
reflux ratio 6.0 ratio of polar to main feed (mol/mol) 2:100
reboiler duty (MW) 1.848 stage location of C4 feed 26
Damköhler number 2.61 stage location of polar feed 6

work begins with the process analysis of reactive distillation in RD eliminates the extraneous cooling requirement by effectively
order to study the influence of important design and operating using the heat of reaction for vaporization of the liquid phase
parameters. For the other multiunit configurations being con- on the reactive trays.
sidered, unlike RD, the operating conditions for the reaction Although the base-case configuration and the resulting column
and distillation steps are independently analyzed and selected. profile shown here are obtained in the presence of polar
Potential configurations are generated for all the selected process components, they are similar to the case in the absence of polar
alternatives over a wide range of conversions. The configurations components.5 This is not surprising, because the amount of polar
are then compared on the basis of the DIB selectivity achieved component used throughout the analysis done in this work is
and cost incurred at identical conversions. very small. However, even small amounts of polar components
can severely reduce the reaction rate, and hence, a higher catalyst
Process Analysis of Reactive Distillation loading is required in order to obtain the same conversion as in
the nonpolar case. It is to be noted that the presence of polar
Modeling Fundamentals. The reaction is conducted in a
components always leads to a better selectivity toward DIB than
hybrid reactive distillation column where the reactive zone lies
that for the nonpolar case, which coincides with the observation
between the rectifying and stripping sections. The widely used
of the kinetics study.14 Hence, throughout this work, polar
equilibrium stage model is applied. The activity and fugacity
components are being used with the view that the increase in
coefficients are calculated using the modified UNIFAC method10
selectivity offered by the addition of polar components out-
and the Peng-Robinson-Stryjek-Vera equation of state,11
weighs the additional costs incurred due to a higher catalyst
respectively. The kinetic model for the dimerization reaction is
loading and separation of the polar components from the final
taken from Honkela and Krause,12 who considered the following
product. It should be noted that polar components have also
two reactions simultaneously in their experiments:
been applied in the industrial plant NExOCTANE technology.
Reaction 1: 2IB f DIB For process development, the influence of various parameters
on the RD configuration needs to be studied. Though similar
Reaction 2: DIB + IB f TIB work has been done with respect to a nonpolar base-case
configuration,5 the influence of the most important parameters
The corresponding rate expressions are is restudied in this work using the polar base case as the
reference.
kDIBaIB2
r1 ) (1) Effect of Number of Reactive Stages. For this analysis, the
(aIB + BTBAaTBA + Bsolventasolvent)2 numbers of rectifying and stripping stages are fixed at 3 and 4,
respectively, according to the separation requirements, and only
kTIBaIBaDIB the number of reactive stages is varied. The C4 feed is introduced
r2 ) (2) at the bottom-most (last) reactive stage, while the polar feed is
(aIB + BTBAaTBA + Bsolventasolvent)3
introduced at the topmost (first) reactive stage. Figure 3 shows
the effect of number of reactive stages in the RD column on
The column model is formulated as a system of differential-
the IB conversion and the DIB selectivity. Both conversion and
algebraic equations and solved using the DIVA simulation
selectivity continue to increase as the number of reactive stages
environment.13
is increased. However, the improvement in selectivity is
Base-Case Configuration. A base-case configuration (Table
insignificant after 5 reactive stages, and this is the same case
1) for the RD process is generated by trial and error, which is
close to a set of optimum parameters and is considered as a
potential RD configuration. Under such conditions, more than
90% IB conversion as well as DIB selectivity is achieved
because of the synergetic effects of reaction and distillation.
The corresponding composition profiles in the column are shown
in Figure 1.
Because of the high exothermicity of the dimerization
reaction, for standard reactor types, it is extremely difficult to
maintain the temperature within the permissible limits unless a
sufficient amount of external cooling is provided. This fact is
demonstrated through a sample temperature profile in an
“almost-adiabatic” plug-flow reactor for a typical simulation
with 40 mol % IB in the C4 feed. As can be seen in Figure 2a,
the temperature increases continuously along the length/volume
of the reactor. An amount of external cooling was intentionally
provided so that temperature does not increase beyond permis-
sible limits of ∼383 K. On the contrary, as shown in Figure
2b, RD provides an almost-constant temperature profile in the Figure 1. Composition profile for the base case (shaded region indicates
reactive zone even without any sort of external cooling. Thus, the reactive zone).

Figure 2. Demonstration of the automatic temperature control in reactive
distillation. (a) Temperature profile in a plug-flow reactor. (b) Temperature
profile in reactive distillation column (shaded region indicates the reactive
zone).
Figure 3. Effect of the number of reactive stages on reactive distillation
column performance.
with conversion beyond 20 reactive stages. To obtain the best
possible combination of the DIB selectivity and IB conversion,
23 reactive stages were finally selected for the base case.
Effect of Location of C4 Feed. Heuristics on RD generally
recommend that, if the reactants are the most volatile compo-
Ind. Eng. Chem. Res., Vol. 45, No. 8, 2006 2709
Figure 4. Effect of the location of C4 feed on reactive distillation column
performance.
Figure 5. Effect of the location of C4 feed on DIB selectivity (IB conversion
fixed at 90% by suitably changing the catalyst loading).
nents in the system, as is the case here, the feed should be
introduced near the bottom of the reactive zone. So for this
analysis, while the location of the polar feed is fixed (as the
base case), the C4 feed location is moved from stage number
16 (near the center of the reactive zone) down to stage number
28, i.e., two stages below the reactive zone of the base case.
As seen in Figure 4, the IB conversion shows an optimum at
stage number 23 while the DIB selectivity continuously
increases. An optimum feed location cannot be selected based
on this result. However, it could be reasoned from Figure 4
that the optimum feed location should lie anywhere between
and including stages 23-28. As both conversion and selectivity
change in the opposite direction from the 23rd stage onward,
the following strategy is employed. While the C4 feed location
is varied, the catalyst loading is changed in order to obtain the
same IB conversion of 90%. As a result, the variation of DIB
selectivity with C4 feed location is now shown in Figure 5. The
maximum selectivity is obtained at the optimum C4 feed
location, i.e., stage 26.
Effect of Column Pressure. The dimerization reaction is
generally conducted in the temperature range of 313-393 K,
while C4 boils in that temperature range under the approximate
pressure range of 6-18 atm. Hence, the effect of pressure on
2710 Ind. Eng. Chem. Res., Vol. 45, No. 8, 2006
Figure 6. Effect of the operating pressure on reactive distillation column
performance.
Figure 7. Effect of the reflux ratio on reactive distillation column
performance.
the performance of the RD column has also been studied in
this pressure range, as shown in Figure 6. As pressure is
increased, the IB conversion increases because of higher reaction
rates. It worth noting that no sharp change in the DIB selectivity
is observed. Instead, it remains close to 95% throughout the
pressure range. For standard batch or continuous reactors,
experimental investigations showed lower DIB yields as com-
pared to simulation results of RD, but quantitative comparisons
are not possible because of the absence of adequate infor-
mation.15-17 Moreover, the bifurcation diagram shows a steady-
state multiplicity in a narrow pressure range near 8.8 atm. A
pressure of 15 atm was selected for the base case as it provides
a better combination of DIB selectivity and IB conversion, both
of which exceed 90%.
Effect of Reflux Ratio. The effect of reflux ratio is studied
for a fixed value of the reboil ratio of 10.0, as used in the base-
case configuration. The column performance is shown in Figure
7, which shows lower IB conversion at lower reflux ratios.
Hence, it is advisable to operate the reactive distillation column
at a relatively high reflux ratio to ensure satisfactory perfor-
mance.
Effect of Catalyst Loading. Catalyst loading is the only
parameter which is significantly affected by the presence of polar
Figure 8. Effect of the catalyst loading on reactive distillation column
performance.
components. For this analysis, the catalyst loading is represented
in the form of Damköhler number (Da), defined as
WTkhet
f,ref
Da ) (3)
FT
where FT is the total feed flow rate to the column, WT is the
het
total amount of catalyst in the column, and kf,ref is the forward
rate constant evaluated at a reference temperature which is
conventionally the lowest-boiling pure component in the system
(i.e., boiling point of isobutene at the column pressure). The
catalyst loading is equally divided on the reactive stages. Da is
varied from zero (i.e., nonreactive distillation) to 16 (∼99%
conversion of IB), as shown in Figure 8. With an increase in
catalyst loading, the IB conversion increases sharply in the initial
period, but beyond Da ) 4.0, a large increase in catalyst loading
is required for a small amount of further improvement in IB
conversion. The selectivity to DIB decreases from near 100%
at very small Da values to about 93% at Da ) 16. The final
choice of Da ) 2.61 in the base case depends on a compromise
between conversion and selectivity.
Selection of Process Conditions for Multiunit
Configurations
The process alternatives other than RD that are considered
in this work do not involve simultaneous reaction and separation.
Hence, for these process alternatives, operating conditions for
reaction and separation can be determined independent of each
other. For a fair comparison, an effort must be made to optimize
the conditions for the reaction and separation units for better
performance.
Reaction Temperature. As stated earlier, the dimerization
reaction is highly exothermic such that external cooling is almost
inevitable when RD is not utilized. If external cooling can be
manipulated favorably, the question arises as to whether there
is a need to maintain any particular temperature profile in the
reaction unit. This question can be best answered through the
use of optimization techniques. However, for a preliminary
analysis, a constant temperature profile (i.e., isothermal condi-
tions) within the reaction unit is assumed.
Now, a constant operating temperature for the reactor needs
to be selected that can give the best-possible performance. It
can be expected, based on the nature of the dimerization

Figure 9. Effect of the reaction temperature on DIB selectivity in a tanks-
in-series reactor (IB conversion fixed at 90% by suitably changing the
catalyst loading).
reaction, that a lower temperature will lead to a lower IB
conversion but a higher DIB selectivity and vice versa for a
higher temperature. However, this fact does not allow us to
select the best-possible operating temperature. Hence, in the
following analysis, the variation of the DIB selectivity with
temperature was studied using a tanks-in-series reactor model
(eight tanks) while maintaining the DIB conversion constant
of 90% by suitably changing the catalyst loading. The analysis
suggests that, at the same IB conversion, a higher operating
temperature always leads to a better DIB selectivity (Figure 9).
This result seems a bit surprising, since the general belief is
that oligomerization increases at higher temperatures and, hence,
should reduce the selectivity. However, it can be reasoned that
the use of higher operating temperatures leads to a lower catalyst
loading for the same conversion. A lower catalyst loading
implies that a lesser number of active catalytic sites are available
for further oligomerization reaction and also that there is a better
“wettability” of the catalyst because of the larger value of the
weight ratio of the polar component to the catalyst. Thus, for
the same conversion, the use of a higher temperature and lower
catalyst loading seems more advantageous than using a lower
temperature and high catalyst loading. Considering the thermal
stability limit of the ion-exchange resin catalyst (120 °C), a safe
design value of 90 °C is being used to represent the optimum
temperature for the reactor unit in all the multiunit configurations
considered in this work.
Reactor Type. The type of the reactor to be used in the
multiunit configurations also needs to be identified. The use of
a single liquid phase is recommended for a better flexibility of
operation, and to maintain liquid conditions, a sufficiently high
pressure (>15 atm) needs to be applied. The simplest reactor
model that can be used is a continuous stirred tank reactor
(CSTR). For heterogeneously catalyzed reactions, the reactor
model is expected to represent a typical industrial packed or
fixed-bed reactor. In that case, the obvious choice is a pseudo-
homogeneous plug-flow reactor (PFR). Another good choice
is the tanks-in-series model, which consists of several consecu-
tive CSTRs in which the product of one reactor is led to the
next one with or without controlling the intermediate conditions.
All the discussed reactor models are compared on the
selectivity vs conversion graph at a constant operating temper-
ature of 90 °C, as shown in Figure 10. As expected, the ideal
CSTR gives the worst performance and, hence, can be elimi-
nated from all further analysis. The ideal PFR shows the best
Ind. Eng. Chem. Res., Vol. 45, No. 8, 2006 2711
Figure 10. Effect of the reactor type on performance (temperature fixed
at 90 °C and changing the catalyst loading).
performance, and the performance of the tanks-in-series model
is between those of the CSTR and the PFR. However, if a
sufficient number of tanks (i.e., 8-10) are used, the performance
of the tanks-in-series model is very close to that of the PFR. It
was also observed that unsteady-state equations for the tanks-
in-series model created less convergence problems as compared
to the PFR model, which involves partial differential equations
in order to predict the variation with respect to time as well as
length/volume of the reactor. Another advantage of the tanks-
in-series model is that it is very convenient to impose a user-
defined temperature profile in the reaction unit by assigning
the desired constant operating temperatures to the various CSTR
units in the reactor train. Because of the above advantages, the
eight-tanks-in-series model is used to represent the reactor unit
in the multiunit configurations. It is to be noted that the tanks-
in-series model has also been used by other researchers, in
particular, to represent the side reactor.6-7
Separation Unit. Even though the RD column employed in
this work operates at a pressure of 15 atm, it is not necessary
for the distillation column in multiunit configurations to be
operated at such a high pressure. It is commonly known that,
as pressure increases, the volatility difference between the
components decreases. Therefore, it is advantageous to perform
the separation at the lowest acceptable pressure, considering
the limit imposed by the coolant used in the condenser. If
cooling water at ambient conditions is to be used to minimize
operating costs and the top product is almost pure C4, then a
pressure of ∼6 atm (or higher) as adopted here was found to
be appropriate for a reasonable heat transfer rate in the
condenser.
Because of the large difference in the volatilities of the
reactants (C4) and the products, it is found that a column
consisting of even 10 stages is sufficient to separate the C4 from
the other products. The separation is based on the predefined
specifications for the compositions of the bottom and top
streams, i.e., almost the entire C4 cut leaves from the top while
the dimer and other oligomers leave from the bottom of the
separation unit. The exact numbers of stages in the rectifying
and stripping sections depend on the location of feed(s) and
side streams, if any.
Structure of the Multiunit Configurations
The first multiunit configuration considered is the conven-
tional process (Figure 11). The C4 and the polar feeds are
2712 Ind. Eng. Chem. Res., Vol. 45, No. 8, 2006
Figure 11. Conventional reaction-separation configuration with/without
recycle.
Figure 12. Configuration of distillation coupling with side reactor.
introduced into the dimerization reactor operating at high
pressure and liquid conditions. The reactor effluent containing
the unreacted IB, inert C4, the desired dimer, and the undesired
oligomers is led to a distillation column where C4 and the rest
of the components are separated as the top and bottom products,
respectively. A part of the top product, if necessary, may be
recycled back to the reactor to increase the overall conversion.
Since the difference between the operating pressure of the
reactor and the distillation column is >7 atm and the C4 feed
used contains ∼60% inerts, it is very likely that the reactor
effluent will flash because of the reduction of pressure. The
extent of flash depends on the amount of IB conversion that
occurs in the reactor, because the formation of high-molecular
products (DIB and oligomers) will increase the bubble-point
temperature of the reactor effluent. To account for this eventual-
ity, a flash unit is also placed between the reactor and the
distillation column (not shown in Figure 11) which detects the
occurrence of the two phases based on the bubble-point
temperature of the reactor outlet evaluated at the distillation
pressure.
The second process alternative considered is the side-reactor
configuration (Figure 12). It is to be noted that, the lesser the
amount of DIB in the feed to the side reactor, the better will be
the overall selectivity, because further loss of selectivity due to
the oligomerization of the DIB in the feed can be avoided. It is
evident that the top stage, i.e., the condenser, contains the least
amount of DIB as compared to any other stage in the column.
Hence, it is clear that recycling a part of the top product as the
feed to the side reactor will give a better performance than using
a side-draw from stages below the condenser. It is found that
10 stages in the distillation column are sufficient for the
Figure 13. Comparison of processes on the basis of performance.
separation even if the side reactor was applied. The polar
component should always be introduced as a separate feed into
the side reactor and not into the column, because if introduced
into the column, due to its low volatility, it will never achieve
a significant concentration in the top product, a part of which
acts as a feed to the side reactor. However, the main C4 feed
can be introduced either into the reactor or into the column.
Since introducing the main feed into the side reactor will actually
be the same as the conventional configuration with recycle, the
main feed is introduced into the distillation column for the side-
reactor configuration analyzed in this work.
The multiunit flowsheets are also solved using the DIVA
simulation environment. The modeling philosophy of DIVA
takes into account the modular topology of chemical engineering
flowsheets. Dynamic models for each of the process units are
written and integrated into the overall plant model forming a
large system of differential algebraic equations.
Comparison of Process Alternatives
As stated earlier, the presence of two criteria for performance,
i.e., IB conversion and DIB selectivity, makes it difficult to
compare the processes. One of the best approaches at such a
preliminary stage is to generate potential configurations of the
processes at various fixed values of conversion and then
compare them on the basis of the best possible selectivity those
configurations can achieve. Since, for a given conversion, a
process alternative may give different values of selectivity
depending upon the choice of design and operating parameters,
the parameters need to be altered in such a way that constraints
on the top and bottom product composition specifications are
never violated, i.e., the dimer composition in the top should
not exceed 1 ppm and almost the entire C4 cut is withdrawn
from the top. Moreover, in this work, we attempted to generate
the best possible combination of design and operating parameters
for a particular process and a specified conversion using the
aid of repeated simulations and knowledge gained from the
trends and behavior of various parameters involved. The work
finally results in a set of >10 configurations for each process,
each of which is judiciously optimized for a particular IB
conversion in the range of 50-95%.
The performance of the processes is compared on the DIB
selectivity vs IB conversion graph, as shown in Figure 13. It
can be seen that, at low conversions (<55%), all the processes
give almost similar selectivities. However, as conversion
 Ind. Eng. Chem. Res., Vol. 45, No. 8, 2006 2713

increases, the differences between the selectivities become more

evident. The RD process gives the best performance with a small
reduction in selectivity for an increase in conversion. This shows
that the RD process has a relatively better flexibility, compared
to other alternatives, in maintaining a high selectivity even at
high conversions by making appropriate changes in the column
parameters.
The conventional processes, both with and without recycle,
perform similar to each other but give a lower selectivity as
compared to the RD process. Here, the amount of recycle is a
crucial parameter and was observed to affect the selectivity
significantly. A high value will force the inert C4 down into
the column, which requires a large adjustment in the other
column parameters, particularly the reboiler duty, in order to
maintain the bottom product specifications. On the other hand,
a low value will not make a significant difference between the
per-pass and the overall conversion. It is to be noted that the
conventional process with recycle considered in our work is Figure 14. Comparison of processes on the basis of cost.
similar to the side-reactor configuration of Ouni et al.7 However,
their results show that the side-reactor processes considered in
their work are better than the RD process, which is in direct a lower cost as compared to the RD process for all the
contradiction with this work. It is very difficult to verify their conversions considered. This does not imply that the conven-
claim because of the lack of information on their feed conditions tional processes are definitely better than RD, since RD offers
(i.e., flow rate, composition, etc.) and the kinetics used, which a better selectivity for the same conversion and the profits due
have a significant impact on the simulation results. to the improved selectivity are not taken into account in the
costing done here because of the variation in the prices of the
The performance of the side-reactor configuration seems to
reactants and products worldwide. Several other factors, such
be an interesting result. The selectivity drops sharply as
as cost of recycling, cost of catalyst regeneration, cost variation
conversion is increased. In terms of performance, particularly
due to time, and geographical location, are not explicitly
at higher conversions, it stands no chance against the RD and considered. However, this can be made more accurate at a
the conventional process. It is to be noted that the composition further stage of process evaluation.
of IB in the feed of the side reactor depends on the top product
composition of the distillation column. As the overall conversion
increases, the isobutene in the top product of the column also Conclusions
decreases, and as we observe, a lower selectivity results. Since
This work attempts to compare the reactive distillation process
the selectivity can be attributed only to the reactor unit because
with other multiunit processes such as the conventional reaction-
no reaction takes place in the column, it seems that the reduction
separation process with/without recycle and the process of
of composition of IB in the feed to the reactor will also decrease
distillation with side reactor, a popular alternative to RD. In
the selectivity.
this framework, the process analysis of the RD configuration
Although the processes have been compared on the basis of was initially carried out, and the influence of important design
performance, it is quite possible that choosing a particular set and operating parameters was identified. The RD process
of design and operating parameters may also lead to a large demonstrates reasonable temperature control, which is extremely
additional operating or capital cost in trying to achieve that extra difficult to achieve in conventional reactor types without external
increment in performance. Hence, comparison of the processes cooling.
on an economic basis is also essential. Here, the equations for The process conditions for the reaction and separation units
cost estimation are obtained from Kaymak and Luyben,9 and for the multiunit configuration were independently identified
costs are estimated based on the configurations corresponding and judiciously selected based on rules of thumb and chemical
to each point in Figure 13. Some of the important factors engineering fundamentals. The reactive distillation process and
influencing the costing are as follows: (1) The RD column uses its competitive multiunit alternative processes are compared first
a total of 30 stages, while the distillation column in the other on the basis of DIB selectivities at the same IB conversion and
processes contains a maximum 10 stages. (2) The multiunit then on the basis of total annual cost at different fixed values
configurations involve extra capital cost for the reactor. of IB conversion. The RD process stands out as the best process
The economic comparison of the processes is shown on a alternative in terms of performance, but the conventional
total annual cost vs conversion graph in Figure 14. As can be processes with and without recycle are equally competitive when
seen, at lower conversions, all the processes seem competitive, cost calculations are also considered. Profits due to the selectiv-
but at higher conversions, there are noticeable differences. The ity enhancement, which are not included in the cost estimation,
reason for the high cost for the side-reactor configuration at may be required for the final selection of the best process
higher conversions is that, because of the high conversion, the configuration for the dimerization reaction.
feed to the side reactor contains much less isobutene, and this
leads to a severe reduction of the rate of reaction. So, a
Acknowledgment
ridiculously large catalyst loading is required to achieve high
conversions. The profile for the RD process shows some sort The financial support for this work from the Volkswagen
of a maximum in the total annual cost. This could be due to Foundation in Germany (VW Stiftung Project “Coupling of
the random selection of the column parameters done for the Chemical Reactions in a Reactive Distillation Process”, AZ
comparison of the processes. The conventional process offers I/79515) is gratefully acknowledged.
2714 Ind. Eng. Chem. Res., Vol. 45, No. 8, 2006
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ReceiVed for reView October 3, 2005
ReVised manuscript receiVed February 9, 2006
Accepted February 15, 2006
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