Ind. Eng. Chem. Res.

2004, 43, 2493-2507 2493

PROCESS DESIGN AND CONTROL

Quantitative Comparison of Reactive Distillation with Conventional

Multiunit Reactor/Column/Recycle Systems for Different Chemical
Equilibrium Constants
Devrim B. Kaymak and William L. Luyben*
Process Modeling and Control Center, Department of Chemical Engineering, Lehigh University,
Bethlehem, Pennsylvania 18015

Recent advances in technologies based on process intensification offer different design alternatives
for chemical processes including reaction and separation units. An excellent example of process
intensification is reactive distillation, which combines reaction and separation units in one piece
of equipment. This paper studies the steady-state economic optimum design of a chemical process
with a generic exothermic reversible reaction A + B T C + D for two different process
flowsheets: a conventional multiunit reactor/separator/recycle structure and a reactive distillation
column. Each system is optimized in terms of the total annual cost for a wide range of chemical
equilibrium constants, KEQ. In the conventional system, the design optimization variables include
the reactor temperature, reactor size, and recycle flow rate. In the reactive distillation system,
the design optimization variables include the pressure, number of reactive trays, and number
of total trays. The two systems are designed for identical feeds and identical products. Results
show that reactive distillation is significantly less expensive (by a factor of up to 3) than the
conventional process for all values of the chemical equilibrium constant.

1. Introduction tants remain in the column. This means that the

If one of the most important operations in chemical
engineering is separation, with distillation columns as
its most popular process unit, reactors are the other
vital parts of the chemical industry. Since reactor
effluents fail to meet specification criteria because of
the presence of unconverted materials, reactors followed
by several distillation columns with recycle streams
back to the reaction section are common in industry.
Economic and environmental considerations have
encouraged industry to focus on technologies based on
process intensification. This is an area of growing
interest that is defined as any chemical engineering
development that leads to a substantially smaller and
more energy-efficient technology.1 An excellent example
of process intensification is reactive distillation, which
combines reaction and separation units in a single
vessel. Reactive distillation can, in some systems,
provide an alternative to conventional multiunit flow-
sheets, which typically include a reactor followed by a
separation section with recycles back to the reaction
section.
Although reactive distillation might be an attractive
alternative to the conventional multiunit processes, it
can be effective for only a fairly small class of chemical
systems because of some inherent limitations. The
relative volatilities of the reactants and the products
should be such that the products can be removed from
the reaction zone of the column easily while the reac-
* To whom correspondence should be addressed. Tel.: 610-
758-4256. Fax: 610-758-5057. E-mail: wll0@lehigh.edu.
10.1021/ie030832g CCC: $27.50 © 2004 American Chemical Society
Published on Web 04/17/2004
products should be lighter or heavier than the reactants.
The temperatures of reaction and separation should be
similar because both of these operations occur in the
same unit simultaneously. The reaction should be fairly
fast, so that the liquid holdups or amounts of catalyst
required on each reactive tray are feasible in light of
hydraulic limitations (reasonable tray liquid heights).
Heats of reaction cannot be too large because of their
impact on the vapor and liquid flow rates throughout
the reactive zone. For example, if the reaction is
exothermic, the liquid flow rates decrease from tray to
tray down through the reactive section of the column,
and the vapor flow rates increase from tray to tray up
through the reactive section. If the heat of reaction is
large, hydraulic problems such as weeping or flooding
can occur.
If reactive distillation is suitable for a chemical
system, then this process provides several advantages
over the conventional flowsheet. Because products are
continuously removed from the reactive zone, the con-
version can increase significantly. The selectivity can
also be increased because of the continuous separation
between reactants and products. A reduction of total
investment and operating costs is usually achieved
through the simplification of the process flowsheet by
the elimination of some process units and direct heat
integration between reaction and separation in the same
vessel.
On the other hand, because reactive distillation
systems have a smaller number of control degrees of
freedom than conventional multiunit reactor/separation/
2494 Ind. Eng. Chem. Res., Vol. 43, No. 10, 2004
recycle systems, they can have worse dynamics, and
their controllability can be more difficult. For a given
feed flow rate, a reactive distillation column has the
same control degrees of freedom as a single conventional
column (four control valves give four control degrees of
freedom). A conventional multiunit flowsheet has four
control degrees of freedom for each column, plus the two
control valves on the reactor (coolant flow rate and
reactor effluent).
One of the most fundamental differences between
reactive distillation and a conventional flowsheet is the
selection of operating temperatures. In the conventional
system, the reactor temperature can be set at an
optimum value, and the distillation temperatures can
be independently set at their optimum values (by
adjusting column pressures). In reactive distillation,
these temperatures are not independent. Therefore,
reactive distillation has fewer design degrees of freedom
to be used to optimize the flowsheet.
The application of reactive distillation in the chemical
and petroleum industries has increased rapidly in the
past decade.2 Following the pioneering paper3 published
by Eastman Chemical discussing the reactive distilla-
tion of methyl acetate, many other papers and patents
have explored the use of this process for other chemical
operations. A number of specific chemical systems have
been studied in the literature. Chapter 10 of the recent
textbook by Doherty and Malone4 presents an excellent
summary of 61 different reactive distillation systems.
Another list of industrial applications of reactive distil-
lation with 75 examples is given in the first chapter of
a recent book on reactive distillation.5 This work states
that the most common applications of reactive distilla-
tions are etherification and esterification reactions.
Although reactive distillation can be effectively used for
systems with a wide variety of chemical equilibrium
constants, the normal range of values for KEQ is between
1 and 50.
Because a reactive distillation column has more
design variables than a conventional column, the design
of such systems is more difficult. The column pressure,
the catalyst holdup on each tray, and the positions of
the feed trays are important design considerations. In
addition to stripping and rectifying sections, there is one
more column section (the reactive zone). Also, the
assumption of constant molar overflow is not valid if
the reactions are not thermally neutral. Several papers
have optimized reactive distillation columns by mini-
mizing the objective function in terms of total annual
cost (TAC).6-10 All of these papers proposed different
optimization methods for reactive distillation systems
and illustrated their methods with examples of specific
chemical systems.
Only a few papers have appeared in the literature
that compare reactive distillation flowsheets with other
process flowsheets.11-13 Siirola11 claimed that both the
capital and energy costs of the reactive/extractive distil-
lation column design for methyl acetate production are
5 times lower than those of the conventional design. The
results in terms of TAC reported by Chiang et al.12 for
the amyl acetate process indicated that reactive distil-
lation is 4 times more efficient than the coupled reactor/
separator system. However, Stitt13 claimed that reactive
distillation for toluene disproportionation did not offer
significant economic benefits.
The purpose of this paper is to quantitatively compare
the designs of two different process flowsheets: (1) a
conventional multiunit reactor/separator/recycle struc-
ture and (2) a reactive distillation column. Both of the
flowsheets are designed to achieve the steady-state
economic objective of minimum total annual cost for a
wide range of chemical equilibrium constants, KEQ.
Systematic design procedures for both flowsheets are
developed as three-dimensional optimization problems
with some heuristic rules and engineering assumptions.
The effects of design parameters on the optimum design
variables and total annual costs are studied for both
process designs. The two flowsheets have identical feeds
and produce identical products.
The vapor-liquid equilibrium used in this paper is
ideal with constant relative volatilities. The rationale
for considering ideal systems is to start with a simple
system in which the complexities of nonideality do not
cloud the issues and the results and some general
conclusions are possible. The occurrence of azeotropes
is very specific to the particular chemical system
considered. We wish to strip away such complexities so
that the fundamental differences between the two
flowsheets can be fairly compared. Future work will
explore the impact of temperature-dependent relative
volatilities on the two processes. It is expected that there
will be a significant effect on the comparison because
of the coupling of the distillation temperatures and the
reaction temperatures in the reactive distillation pro-
cess. In the conventional flowsheet, the reactor temper-
ature and the column temperatures can be set indepen-
dently.
2. Process Studied
The basic process considered consists of a reversible
liquid-phase reaction
A+BSC+D (1)
The forward and backward specific reaction rates,
following the Arrhenius law, are given by
kF ) aFe-EF/RT (2)
kR ) aRe-ER/RT (3)
The rate law is based on concentrations in mole frac-
tions and liquid holdups in kilomoles. The forward
reaction rate is specified as 0.008 kmol s-1 kmol-1 at
366 K. Taking (KEQ)366 equal to 2 as a base case, the
reverse reaction rate at this temperature is varied by
selecting a range of (KEQ)366 values between 0.5 and 50.
(kF)366
(kR)366 ) (4)
(KEQ)366
Therefore, for different values of (KEQ)366, different
values of the preexponential factor aR are calculated.
Both reaction rates are temperature-dependent, and the
reverse reaction rate is different for each case of (KEQ)366
selected. Note that the ratio of kF to kR is not equal to
(KEQ)366 at temperatures other than 366 K because the
activation energies are different. Rather, because the
reaction is exothermic, the reverse reaction rate is more
temperature-dependent than the forward reaction rate.
Ideal vapor-liquid equilibrium is assumed with con-
stant volatilities. The volatilities of the components are
such that RC > RA > RB > RD. Hence, the reactants are
intermediate boiling between the two products, which
 Ind. Eng. Chem. Res., Vol. 43, No. 10, 2004 2495

Table 1. Physical Data for the Process 3. Conventional Process Design

parameter units value
Figure 1 presents a detailed flowsheet of the process
reaction activation energy cal/mol with notation. The reaction occurs in a continuous
forward 30 000 stirred tank reactor (CSTR) with holdup VR. There are
reverse 40 000
specific reaction rate at 366 K kmol/(s‚kmol)
two fresh feed streams F0A and F0B that contain pure
forward 0.008 reactants A and B, respectively, and a recycle stream
reverse 0.008/(KEQ)366 D2 that returns from a downstream unit. The reactor
average heat of reaction, λ cal/mol -10 000 effluent contains a multicomponent mixture because
average heat of vaporization, cal/mol 6944 complete one-pass conversion is not achieved. Two
∆HV columns are needed to separate the two products from
molecular weight of the g/mol 50
mixture, Mw the intermediate-boiling reactants. This effluent is fed
ideal gas constant cal/(mol K) 1.987 into the first distillation column to separate product C
relative volatilities from unreacted reactants A and B and heavy product
RA 4 D. The product C leaves in the distillate of first column
RB 2 with the desired purity, and other components serve as
RC 8 a feed to the second column. This column produces a
RD 1
vapor-pressure A B C D
bottoms stream of D with the desired purity, and a
constantsa distillate of unreacted reactants A and B is recycled back
AVP 12.34 11.65 13.04 10.96 to the reactor with a specific amount of product impuri-
BVP 3862 3862 3862 3862 ties.
a ln PSj ) AVP,j - BVP,j/T, with temperature in Kelvin and vapor One of the main problems in developing a steady-state
pressure in bar. process flowsheet is finding the number of design
degrees of freedom, which can be done by subtracting
the number of chemical and physical equations (total
is the ideal situation for reactive distillation. Kinetic and
and component balances, VLE relations) describing the
physical properties and vapor-liquid equilibrium pa- system from the total number of variables (see Table
rameters are listed in Table 1 and are taken from 2). The number of design degrees of freedom for this
Luyben.14 multiunit process is 12. Subtracting the number of
It should be emphasized that the two flowsheets have specifications and safety and environmental constraints
identical feeds and produce identical products. In ad- from the number of degrees of freedom gives the number
dition, the economic factors (energy cost and capital cost of design optimization variables.
of columns and heat exchangers) are the same in the 3.1. Assumptions and Specifications. It is as-
two processes. sumed that there is equimolal overflow in the distilla-

Figure 1. Detailed system flowsheet for the conventional design.

2496 Ind. Eng. Chem. Res., Vol. 43, No. 10, 2004

Table 2. Design Degrees of Freedom

variables equations
compositions component balances
reactors zj 3 reactor 3
tray liquid xn,j 3∑N trays 3∑N
tray vapor yn,j 3∑N bases 6
reflux drums xD,j 6 reflux drums 6
base liquid xB,j 6 total balances
base vapor yB,j 6 reactor 1
flows bases 2
fresh feeds F0,j 2 reflux drums 2
reactor effluent F 1 VLE
vapor boilups Vn 2 trays 3∑N
distillates Dn 2 bases 6
bottoms Bn 2
refluxes Rn 2
reactor holdup VR 1
reactor temperature TR 1
numbers of trays
stripping NS,n 2
rectifying NR,n 2
total number of variables ) 6∑NT + 38 total number of equations ) 6∑NT + 26
number of design degrees of freedom ) 12

tion columns, which means that neither energy balances
nor total balances are needed on the trays for steady-
state calculations. Other assumptions are constant
relative volatilities, isothermal reactor operation, theo-
retical trays, saturated liquid feed and reflux, and total
condensers and partial reboilers in the columns. Ad-
ditional assumptions and specifications are as follows:
(i) In all cases, the net production rates are set by
fixing the fresh feed flow rates of pure components A
and B at F0A ) 12.60 mol/s and F0B ) 12.60 mol/s,
respectively.
(ii) The amount of reactant A lost in product stream
D1 is constant at Aloss ) 0.63 mol/s (xD1,A ) 0.05 mole
fraction). No B or D is going overhead, i.e., xD1,B ) xD1,D
) 0.
(iii) The bottoms product stream B2 contains some
amount of component B as an impurity, Bloss ) 0.63
mol/s (xB2,B ) 0.05 mole fraction). No A or C is going
out the bottoms, i.e., xB2,A ) xB2,C ) 0.
(iv) The impurity of product C in recycle stream D2 is
xD2,C ) 0.05.
(v) The impurity of component D in recycle stream
D2 is xD2,D ) 0.05.
(vi) As a result of the previous two assumptions and
the fact that C and D have identical stoichiometric
coefficients, the concentrations of components C and D
in the reactor, zC and zD, are equal for all cases (zC )
zD) but vary in value from case to case.
(vii) The column pressures are set using the vapor
pressures, PS, of pure components and the liquid
compositions in the reflux drum, xD,j, at 320 K (so that
cooling water can be used in the condenser).
(viii) In each column, the reflux ratio, RR, is 1.2 times
search with the following optimization variables: (1) the
molar holdup in the reactor VR, (2) the composition of
reactant B in the reactor zB, and (3) the reactor
temperature TR.
Also, several different specifications for assumptions
ii-v are used to investigate the effects of product
quality, conversion and recycle impurities on the eco-
nomically optimal steady-state design. However, these
variations do not affect the general structure of the
design procedure.
A grid-search optimization strategy is used in this
work to find the optimum values of the three design
optimization variables. Other methods, such as gradient
nonlinear programming techniques, could be used.
However, the grid method is more robust because a
numerical programming method can easily drive the
process into an infeasible region in which the specified
purities and production rates cannot be achieved.
3.2. Steady-State Design Procedure. The following
steps in the design procedure are employed utilizing the
material balances and specifying necessary variables.
The production rates of components C and D (RC and
RD) are given by
RC ) RD ) VR(kFzAzB - kRzCzD) (5)
(i) Fix the value of reactor temperature TR at a small
value.
(ii) Fix the value of reactor holdup VR at a small value.
(iii) Specify the value of reactor composition zB.
(iv) Using the assumption of equal compositions zC
and zD in the reactor, calculate the concentration zA by
rearranging eq 5 to give

{
the minimum reflux ratio, RRmin, calculated via the
Underwood equations.
1 kF
(ix) In each column, the number of stages (or trays), zA ) 4 z + 2(1 - zB) (
2 kR B

]}
NT, is twice the minimum number of stages, NTmin,

x[ ] [
calculated via the Fenske equation. kF 2 RC
(x) Kirkbride’s method is used to find the optimal feed 4 zB + 2(1 - zB) - 4 (1 - zB)2 + 4 (6)
tray location, NF.
kR VRkR
Through these assumptions, nine of the design de-
grees of freedom are used as follows: one for the (v) Calculate the product concentrations zC and zD in
production rate, two for product impurities, two for the reactor as
recycle impurities, and four for total tray numbers and
optimum feed tray locations. This reduces the steady- 1 - zA - zB
zC ) z D ) (7)
state economic optimization to a three-dimensional 2
 Ind. Eng. Chem. Res., Vol. 43, No. 10, 2004 2497

(vi) Calculate the distillate product flow rate and

compositions for the first column

D1 ) RC + Aloss (8)

xD1,A ) Aloss/D1 (9)

xD1,C ) RC/D1 (10)

(vii) Calculate the bottoms flow rate and compositions

for the second column

B2 ) RD + Bloss (11)

xB2,B ) Bloss/B2 (12)

xB2,D ) RD/B2 (13)

(viii) Apply a steady-state total molar balance, which

can be used because the reactions are equimolar. This
balance, the two steady-state component balances, and
a mole fraction summation around the reactor are

F0A + F0B + D2 ) F (14)

F0A + D2xD2,A ) FzA + RC (15)

F0B + D2xD2,B ) FzB + RD (16)

xD2,A + xD2,B + xD2,C + xD2,D ) 1 (17)

Figure 2. Reactive distillation column.
Solve these four equations for the four unknowns: the
recycle stream flow rate D2, the reactor effluent flow (xi) Using these data, calculate the total annual cost
rate F, and the reactant compositions in second distillate (TAC) by combining the energy cost with the annual
stream xD2,A and xD2,B. The combination of eqs 14-17 capital cost, using a payback period. All of the terms
yields and equations related to the sizing and economy of the
process are given in section 5.
(F0A + F0B)(zA + zB - 1) + RC + RD (xii) Vary the value of zB over a wide range, and repeat
D2 ) (18) steps iv-xi for each value of zB, generating the corre-
(1 - xD2,C - xD2,D) - zA - zB
sponding TAC.
(xiii) Then, vary the value of the reactor holdup over
F ) F0A + F0B + D2 (19) a range, and repeat steps iii-xii.
(xiv) Finally, vary the value of the reactor tempera-
FzA + RC - F0A ture over a wide range, and repeat steps ii-xiii for each
xD2,A ) (20)
D2 temperature. Select the minimum in the TAC as the
economically optimum steady-state design for the given
xD2,B ) (1 - xD2,C - xD2,D) - xD2,A (21) (KEQ)366 value.

(ix) Use the total mass balance and component
balances around the first column to calculate the
bottoms flow rate and compositions for that column
B1 ) F - D1 (22)
Fzj - D1xD1,j
xB1,j ) (23)
B1
(x) Now that the feed, bottoms, and distillate flow
rates and compositions are known for both columns, use
the Fenske equation to calculate the minimum number
of trays. Set the actual number of trays equal to twice
the minimum. Then use the Underwood equations to
calculate the minimum reflux ratio. For sizing purposes,
set the actual reflux ratio equal to 1.2 times the
minimum value.
4. Reactive Distillation Design
The reactive distillation alternative is shown in
Figure 2. The column is fed with two pure reactant fresh
feed streams: F0A and F0B. The column has three zones.
There are NS trays and a partial reboiler in the stripping
section. Above this section, there is a reactive zone with
NRX reactive trays. The third section is the rectifying
section with NR trays and a total condenser.
Light reactant A is fed to the bottom tray of the
reactive zone, while heavy reactant B is introduced at
the top of the reactive section. Light product C leaves
in the distillate, while heavy product D is removed from
the bottoms. Because the light reactant goes up through
the column after being fed on the bottom tray of the
reactive zone, very little of component A is present in
the bottoms. Likewise, heavy reactant goes down through
the column after being fed on the top tray of the reactive
2498 Ind. Eng. Chem. Res., Vol. 43, No. 10, 2004

zone, so very little of component B is present in the

distillate. Thus, the key components are light product
C and light reactant A for the rectifying section. For
the stripping section, the key components are heavy
product D and heavy reactant B.
4.1. Assumptions and Specifications. The optimi-
zation of a reactive distillation column has a very large
number of design variables. The following are the
specifications and assumptions made to reduce the
number of design variables for the economically opti-
mum steady-state design:
(i) The design objective is to obtain 95% conversion
for fixed fresh feed flow rates of 12.6 mol/s.
(ii) The product impurity of the distillate stream is
xD,A ) 0.05.
(iii) The product impurity of the bottoms stream is
xB,B ) 0.05.
(iv) The two feed points are at the two ends of the
reactive zone.
(v) The holdups are constant on the reactive trays at
1000 mol and in the other sections of the column at 400
mol.
(vi) The numbers of stripping and rectifying trays are
equal because the relative volatilities between the
components being separated in the two sections are the Figure 3. Reactive tray.
same. In the rectifying section, the separation is be-
tween C and A, where the relative volatility is RC/RA )
2, and in the stripping section, the separation is between the liquid flow rate decreases down through the reactive
B and D, where the relative volatility is RB/RD ) 2. zone.
With these specifications and simplifying assump-
λ
tions, there are three optimization variables: (1) the Vi ) Vi-1 - R (25)
column pressure P, (2) the number of reactive trays NRX, ∆HV i,C
and (3) the number of the separating (stripping/rectify-
ing) trays NS (or NR). λ
Li ) Li+1 + R (26)
Specifications ii and iii are changed during the study ∆HV i,C
to investigate the effects of product quality and conver-
sion on the economically optimal steady-state design. The dynamic component balances for the column are
However, this does not affect the general structure of as follows:
the design procedure.
4.2. Steady-State Design Procedure. Simulta- reflux drum
neous solution of the very large set of nonlinear and d(xD,jMD)
algebraic equations is difficult, especially with the high ) VNTyNT,j - D(1 + RR)xD,j (27)
degree of nonlinearity due to reaction kinetics. The dt
relaxation method is efficient and robust in solving this
large set of equations. This method is used to calculate rectifying and stripping trays
mole fractions and temperature profiles through the d(xi,jMi)
column. In general, relaxation methods use the equi- ) Li+1xi+1,j + Vi-1yi-1,j - Lixi,j - Viyi,j (28)
librium-stage model equations in unsteady-state form dt
and integrate them numerically until the steady-state
reactive trays
solution is found. Here, the liquid holdups on the trays
are assumed constant, i.e., instantaneous hydraulics. A d(xi,jMi)
general schematic diagram of an equilibrium tray in the ) Li+1xi+1,j + Vi-1yi-1,j - Lixi,j - Viyi,j + Ri,j
dt
reactive zone, from which the equations for a dynamic (29)
model can be derived, is shown in Figure 3. The net
reaction rate for component j on tray i in the reactive feed trays
zone is given by
d(xi,jMi)
) Li+1xi+1,j + Vi-1yi-1,j - Lixi,j - Viyi,j +
Ri,j ) νjMi(kFixi,Axi,B - kRixi,Cxi,D) (24) dt
Ri,j + Fizi,j (30)
where νj is the stoichiometric coefficient of component
j. column base
The steady-state vapor and liquid flow rates are
constant through the stripping and rectifying sections d(xB,jMB)
because equimolal overflow is assumed. However, these ) L1x1,j - BxB,j - VSyB,j (31)
dt
rates change through the reactive zone because of the
exothermic reaction. The heat of reaction vaporizes some With the equimolal overflow assumption mentioned
liquid on each tray in that section; therefore, the vapor above, all of the vapor rates, Vi, throughout the stripping
flow rate increases up through the reactive zone, and section are equal to VS, and all of the liquid rates, Li,
 Ind. Eng. Chem. Res., Vol. 43, No. 10, 2004 2499

are equal to LS. Analogously, all of the vapor rates, Vi, Table 3. Sizing and Economic Basis
beginning from the top feed tray throughout the rectify- parameter units value
ing section and total condenser are VNT, and all of the
reboiler
liquid rates, Li, are equal to LR. heat-transfer coefficient, UR kJ/(s‚K‚m2) 0.568
The vapor-liquid equilibrium is assumed to be ideal. temperature difference, ∆TR K 34.8
Column pressure P is optimized for each case. With condenser
given pressure P and tray liquid composition xi,j, the heat-transfer coefficient, UC kJ/(s.K.m2) 0.852
temperature Ti, and the vapor composition yi,j can be temperature difference, ∆TC K 13.9
calculated. This is a bubble-point calculation and can energy cost $/106 kJ 4.7
payback period, βpay year 3.0
be solved by a Newton-Raphson iterative convergence
method. can be easily observed from the continuously increasing
NC vapor boilup, and the simulation can be restarted in
P) ∑
j)1
S
xi,jPi,j(T) (32)
such cases with new optimization variables.

5. Sizing and Economic Basis

S
Pi,j The economic basis for the calculations involves an
yi,j ) x (33) objective function that sums the capital and energy costs
P i,j
of the process assuming a payback period (βpay) for
With a fixed value of the kinetic parameter (KEQ)366, capital. Total annual cost is defined as
the following steps in the design procedure are used:
(i) Fix the column pressure P at a small value. capital investment
TAC ) energy cost + (34)
(ii) Fix the number of stripping trays NS and the βpay
number of rectifying trays NR at a small value.
(iii) Specify the number of the reactive trays NRX. Table 3 summarizes the economic parameters and the
(iv) Fix the flow rates of the two fresh feeds at 12.60 basis of the equipment sizing calculations.
mol/s. The capital costs of individual equipment and the
(v) Fix the flow rates of the distillate and bottoms at energy cost are estimated using the following equa-
12.60 mol/s. tions15
(vi) Manipulate the vapor boilup VS with a P control-
ler to control the level in the column base. Do not control reactor cost ) 52 920DR1.066LR0.802 (35)
the reflux drum level.
(vii) Manipulate the reflux flow rate with a PI column cost ) 17 640DC1.066LC0.802 (36)
controller to drive the composition of product C in the
distillate to its desired value. This also sets the purity
of the bottoms product D and the conversion in the tray cost ) 229DC1.55NT (37)
reactive zone to their desired values.
(viii) Compute the vapor compositions and tempera- heat exchanger cost ) 7296AR0.65 + 7296AC0.65 (38)
tures on each tray using bubble-point calculations.
(ix) Compute the reaction rates with eq 24. energy cost ) 0.6206∆HVVS (39)
(x) Calculate the vapor rates using eq 25 and assum-
ing equimolal overflow through the stripping and rec- The terms involved in the TAC equations are calcu-
tifying sections. lated from the following set of assumptions and guide-
(xi) Calculate the liquid flow rates from eq 26 with lines:
the same assumption as in step x. (i) The diameter of the reactor is calculated from
(xii) Evaluate the time derivatives of the component
material balances using eqs 27-31. DR ) (3.977 × 10-5VR)0.3333 (40)
(xiii) Integrate all of the ODEs using the Euler
algorithm. (ii) The reactor length is assumed to be twice the
(xiv) Repeat steps vi-xiii until the system achieves diameter.
the convergence criterion, which is CC ) max |dxi,j/dt|
e 10-6 (the largest time derivative of any component LR ) 2DR (41)
on any tray is less than 10-6).
(xv) With the data obtained, calculate the total annual (iii) Assuming an F factor of 1 in engineering units,
cost (TAC) by combining the energy cost with the annual the diameter of the column is calculated from the
capital cost. equation
(xvi) Vary the number of reactive trays over a wide
range, and repeat steps iv-xv for each value of NRX,
generating its corresponding TAC.
(xvii) Then, vary the number of the stripping and
DC ) 1.735 × 10-2 ( )
MwT
P
0.25
VNT0.5 (42)

rectifying trays over a range, and repeat steps iii-xvi.
(xviii) Finally, vary the value of the column pressure
over a wide range, and repeat steps ii-xvii for each
pressure value. Select the design with the minimum
TAC as the economically optimum steady-state design
for the given (KEQ)366 value.
Depending on the values of optimization variables
chosen, the column can leave the feasible region. This
(iv) The column height is calculated assuming a
0.61-m (2-ft) tray spacing and allowing 20% more height
for base-level volume.
LC ) 0.731 52NT (43)
(v) The heat-transfer areas of the reboiler and con-
denser are calculated using the steady-state vapor flow
2500 Ind. Eng. Chem. Res., Vol. 43, No. 10, 2004
Figure 4. TAC for the base case of (KEQ)366 ) 2.00 with constant
reactor temperature TR ) 367 K.
rates and the heat of vaporization.
VS∆HV
AR ) 0.0042 (44)
UR∆TR
VNT∆HV
AC ) 0.0042 (45)
UC∆TC
The vapor flow rate in the top tray, VNT, is higher than
the vapor flow rate in the reboiler, VS, because of the
liquid vaporized through the reactive section. Thus, the
heat-transfer areas of the reboiler and condenser are
calculated using two different vapor rates.
(vi) The two processes are assumed to be equally
reliable and to operate for 365 days per year.
6. Results and Discussion
6.1. Conventional Process Design. Figure 4 shows
a plot of the total annual cost (TAC) for the base case,
(KEQ)366 ) 2, with the constant reactor temperature TR
) 367 K. The TAC is plotted versus the reactor holdup,
VR, and the composition of component B in the reactor,
zB. The reactor holdup and the reactor composition of
component B were varied in increments of 2.5 kmol and
0.025, respectively, yielding a total of 360 different
designs.
With an in-depth look, Figure 5 displays how several
design parameters are affected by the variation of the
optimization variables VR and zB, and Figure 6 shows
how capital cost and energy cost vary. Both figures are
plotted versus zB for three different values of reactor
holdup VR with the fixed temperature TR ) 367 K.
Figure 5 demonstrates that the reactor effluent
contains a higher concentration of reactant components
as the reactor size decreases. Thus, there is a need of
more vapor boilup to achieve the desired product
specifications and an increase in recycle flow rate with
smaller reactor holdup. Increasing zB decreases zA for
a given reactor holdup. The vapor boilup in the first
column, VS1, decreases because there is less A to be
separated from C. As the value of zB increases, the vapor
boilup in the second column, VS2, starts to increase
because there is more B to take overhead. The process
can be operated at any point on this curve with the same
production rate for this given VR, but the reactor effluent
F, the flow rate of bottoms stream B1, and the flow rate
of recycle stream D2 will vary, as shown in the lower
graphs of Figure 5. There is a value of zB that produces
a minimum reactor effluent flow rate, and this occurs
in the region where the compositions of the two reac-
tants are similar because the reaction rate depends on
the product of the two reactant concentrations. The
optimum design point is shown on each graph as an
open circle.
Figure 6 shows that a larger reactor size results in a
higher capital cost but a lower energy cost because of
the lower vapor boilup requirement for all values of zB.
From the same figure, it is clear that for all reactor
holdups there is a minimum in both the capital cost and
energy cost at a specific value of zB at which the
concentrations of zA and zB are similar. Thus, there
should be a minimum in the total cost around this value
of zB because of the tradeoff between increasing capital
cost and decreasing energy cost.
Figures 7 and 8 provide results for the base case using
a range of reactor temperatures as the third optimiza-
tion variable. All of the results in both figures are the
economically optimal steady-state values at the given
temperature. The specific reaction rates in the reactor
increase with increasing temperatures. Figure 7 shows
that increasing the temperature decreases the reactor
holdup (VR) for a specified rate of production of C and
D. This means that higher temperature results in lower
reactor cost, as shown in Figure 8. On the other hand,
the column cost, the heat exchanger cost, and the energy
cost all depend on the vapor boilups in the system. It
can be seen from Figure 7 that there are minima in the
vapor boilup curves at certain values of reactor tem-
perature. Because the optimum value of VR decreases
with increasing reactor temperature, the per-pass con-
version in the reactor decreases. Thus, the reactor
effluent F contains more reactant components A and B
at higher temperatures. Another reason for the increase
in the reactant contents in the reactor effluent is that
the equilibrium constant KEQ decreases with increasing
temperature for exothermic reactions. More reactants
fed to the columns result in an increase in reflux and
vapor boilup required to achieve the desired purities of
product streams. Therefore, these separation costs
increase when the reactor temperature gets high.
Because of the decreasing reactor cost, the total capital
cost decreases with the increase in temperature up to a
certain value. Figure 8 shows, however, that above this
temperature, the increasing column cost and heat
exchanger cost are more dominant and result in in-
creasing total capital cost.
The total annual cost reaches a minimum at a certain
reactor temperature because of the tradeoff between
reactor cost and separation cost. The optimum reactor
temperature for this base-case value of (KEQ)366 is 367
K. The optimum values of the other optimization
variables at the optimum temperature are VR ) 102.5
kmol and zB ) 0.225. Other important design param-
eters are the recycle flow rate D2 (22.89 mol/s) and the
composition of component A in the reactor (zA ) 0.2296).
Figure 9 presents results for different (KEQ)366 values.
The first graph shows that at higher values of (KEQ)366
the total annual cost (TAC) of the system decreases. The
optimum temperature increases as the value of (KEQ)366
increases. Reactor holdups decrease for all kinetic cases
as the temperatures increase. The lower graphs show
that higher values of (KEQ)366 result in lower values of
the recycle stream and vapor boilup. The curves of the
recycle stream and vapor boilup of second column
exhibit minima at certain values of reactor temperature.

Figure 5. Effects of optimization variables VR and zB for the base case of (KEQ)366 ) 2.00 with the constant temperature TR ) 367 K.
Figure 6. Effects of optimization variables VR and zB on design
costs for the base case of (KEQ)366 ) 2.00 with the constant
temperature TR ) 367 K.
For each kinetic case, the shapes of the curves are
similar, but they have minima at different tempera-
tures. For both low and high temperatures, the increase
of these flow rates occurs because of the higher reactant
compositions in the reactor effluent, as shown in Figure
7 for the base case, (KEQ)366 ) 2. As mentioned before,
higher temperatures give smaller reactor holdups VR
and lower equilibrium constants KEQ, which give higher
reactant concentrations. However, low temperatures
give small specific reaction rates, meaning that more
reactant leaves the reactor. Therefore, higher vapor
boilup is required in the columns to obtain the product
streams with specified purities.
Optimization results for the conventional design for
all cases are summarized in Table 4. These are the
optimum designs in terms of the reactor temperature,
the reactor holdup, and the composition of component
B in the reactor. Optimal operating conditions for the
same cases are reported in Table 5. The column pres-
Ind. Eng. Chem. Res., Vol. 43, No. 10, 2004 2501
Figure 7. Effects of optimization variable TR for the base-case
(KEQ)366 ) 2.00 design.
sures are set using the vapor pressures, PS, of the pure
components at 320 K and the liquid compositions in the
reflux drum, xD,j. In a conventional multiunit process,
the column temperatures can be set independently so
as to optimize column efficiency. The reactor tempera-
ture can then be independently adjusted to its optimum.
This is not the case in reactive distillation because both
reaction and separation are occurring in the same
vessel, operating at a single pressure.
The effect of the conversion design value is explored
by increasing the conversion from 95 to 99%. Increasing
the conversion means that the product purities increase
(less unreacted A and B are lost in the product streams)
and the optimum values of all of the design parameters
change. Figure 10 gives results for all of the (KEQ)366
cases. The vapor boilup required to achieve 99% conver-
sion increases, as does the flow rate of the recycle
stream, D2. The reactor holdups are almost the same
for both conversions. These results illustrate that, as
2502 Ind. Eng. Chem. Res., Vol. 43, No. 10, 2004

Figure 8. Effects of optimization variable TR on design costs for the base-case (KEQ)366 ) 2.00 design.

C and D are simultaneously varied from 0.001 to 0.125.

The TAC decreases with higher amounts of impurities.
The reactor holdup also decreases, whereas the recycle
flow rate and vapor boilup of the second column
increase. Although there is an initial large decrease in
TAC as impurities are increased from 0.001, the change
in TAC is not very significant above an impurity value
of about 0.05. Therefore, xD2,C ) xD2,D ) 0.05 is used as
the base impurity level for other kinetic cases.
6.2. Reactive Distillation Design. Figure 12 shows
the effects of separation stages on the economically
optimum steady-state design of a reactive distillation
column with three different operation pressures. The
results are given for the base case, (KEQ)366 ) 2, with a
number of constant reactive trays, NRX ) 9. The graph
in the middle shows that the column cost increases as
the number of separation trays increase. It also shows
Figure 9. Optimization results for different kinetic cases. that a decrease in the operation pressure results in an
increase in the column cost for any number of separation
Table 4. Optimization Results for the Conventional
Design
trays because decreasing the pressure results in a lower
density, which increases the column diameter. The right
(KEQ)366 graph indicates that the higher the number of separa-
0.5 1.0 2.0 5.0 10.0 50.0 tion stages, the lower the vapor boilup required. More
design variables stripping and rectifying stages provide the required
TR (K) 356.0 362.0 367.0 373.0 379.0 395.0 separation while using less energy. Because the tem-
VR (kmol) 222.5 145.0 102.5 82.5 60.0 25.0 perature of the reactive zone increases with increasing
zB 0.275 0.250 0.225 0.175 0.150 0.110 column pressure, it decreases the chemical equilibrium
capital costs ($103)
reactor 358.6 274.7 221.3 193.3 158.6 91.9
constant, which results in an increase in the amounts
heat exchanger 630.1 565.7 509.6 444.2 407.2 341.3 of reactant leaving the reactive zone. Therefore, the
column 293.3 268.1 245.8 217.9 202.4 175.0 right graph also shows that operating at higher pressure
tray 9.5 8.3 7.3 6.1 5.5 4.4 increases the vapor boilup required to meet desired
energy cost ($103/year) 502.9 425.4 361.9 292.8 256.3 195.7 product specifications. The left graph of Figure 12 shows
TAC ($103/year) 933.4 797.7 689.9 580.0 514.2 399.9
that there is a minimum in the total annual cost curve
at a certain number of separation trays because of the
expected, the TAC of the system increases when a tradeoff between increasing column cost and decreasing
higher conversion is required. costs related to the vapor boilup, such as energy and
Figure 11 shows the effect of impurities in the D2 heat exchanger costs. The overlapping TAC curves for
recycle stream on the total annual cost for the base case, different pressures show that there is an optimum
where (KEQ)366 is 2. The impurities of both components pressure. This occurs because of the competing effects
 Ind. Eng. Chem. Res., Vol. 43, No. 10, 2004 2503

Table 5. Optimal Operating Conditions of Conventional

Design
(KEQ)366
parameter 0.5 1.0 2.0 5.0 10.0 50.0
Reactor
F (mol/s) 66.02 55.81 48.09 40.39 36.65 31.20
VR (kmol) 222.50 145.00 102.50 82.50 60.00 25.00
TR (K) 356.00 362.00 367.00 373.00 379.00 395.00
kF (s-1) 0.0025 0.0051 0.0090 0.0174 0.0329 0.1653
kR (s-1) 0.0034 0.0044 0.0046 0.0045 0.0053 0.0091
zA 0.3005 0.2662 0.2296 0.1947 0.1655 0.1035
zB 0.2750 0.2500 0.2250 0.1750 0.1500 0.1100
zC 0.2122 0.2419 0.2727 0.3151 0.3422 0.3933
zD 0.2122 0.2419 0.2727 0.3151 0.3422 0.3933
Column 1
B (mol/s) 53.42 43.21 35.49 27.79 24.05 18.60
D (mol/s) 12.60 12.60 12.60 12.60 12.60 12.60
VS (mol/s) 50.56 44.57 39.56 34.67 31.66 25.62
R (mol/s) 37.96 31.97 26.96 22.07 19.06 13.02
P (bar) 2.57 2.57 2.57 2.57 2.57 2.57 Figure 10. Effects of conversion for different kinetic cases.
xD,A 0.0500 0.0500 0.0500 0.0500 0.0500 0.0500
xD,B 0.0000 0.0000 0.0000 0.0000 0.0000 0.0000
xD,C 0.9500 0.9500 0.9500 0.9500 0.9500 0.9500
xD,D 0.0000 0.0000 0.0000 0.0000 0.0000 0.0000
xB,A 0.3596 0.3292 0.2933 0.2603 0.2261 0.1397
xB,B 0.3399 0.3229 0.3049 0.2543 0.2286 0.1845
xB,C 0.0382 0.0354 0.0322 0.0273 0.0238 0.0161
xB,D 0.2623 0.3124 0.3695 0.458 0.5215 0.6596
NT 13 13 13 13 13 13
NF 6 6 7 7 8 8
DC (m) 1.09 1.03 0.97 0.90 0.86 0.78
AR (m2) 74.36 65.56 58.18 50.99 46.57 37.68
AC (m2) 124.11 109.42 97.11 85.10 77.72 62.90
Column 2
B (mol/s) 12.60 12.60 12.60 12.60 12.60 12.60
D (mol/s) 40.82 30.61 22.89 15.19 11.45 6.00
VS (mol/s) 66.14 54.15 44.42 33.28 27.82 19.80
R (mol/s) 25.33 23.54 21.54 18.09 16.37 13.80
P (bar) 1.00 0.99 0.98 1.00 1.00 0.97
xD,A 0.4706 0.4648 0.4548 0.4762 0.4749 0.4331
xD,B 0.4294 0.4352 0.4452 0.4238 0.4251 0.4669
xD,C 0.0500 0.0500 0.0500 0.0500 0.0500 0.0500
xD,D 0.0500 0.0500 0.0500 0.0500 0.0500 0.0500 Figure 11. Effects of impurities in the recycle stream for the base
xB,A 0.0000 0.0000 0.0000 0.0000 0.0000 0.0000 case of (KEQ)366 ) 2.0.
xB,B 0.0500 0.0500 0.0500 0.0500 0.0500 0.0500
xB,C 0.0000 0.0000 0.0000 0.0000 0.0000 0.0000
xB,D 0.9500 0.9500 0.9500 0.9500 0.9500 0.9500
NT 13 13 13 13 13 13
NF 8 8 7 7 6 6
DC (m) 1.58 1.43 1.30 1.12 1.03 0.87
AR (m2) 97.29 79.65 65.34 48.96 40.92 29.12
AC (m2) 162.38 132.93 109.06 81.71 68.30 48.61

of temperature on the reaction rates and the chemical

equilibrium constant. For this case, five stripping and
five rectifying trays are optimal for all pressures.
Figure 13 reveals the effects of the number of reactive
trays for the base case with the constant number of
separation stages NR ) NS ) 5. The graph in the middle
shows that increasing the number of reactive trays
results in an increase in the column cost and that higher
pressures lead to a lower column cost for any value of
NRX.
The right graph shows the effects of the number of
reactive stages on the vapor boilup. As the number of Figure 12. Effect of number of separation stages for the base
reactive trays increases, the required vapor boilup case of (KEQ)366 ) 2 with constant NRX ) 9.
initially decreases. However, increasing the number of
reactive trays above the optimum results in an increase cussed by Sneesby and co-workers.16 For example, the
in the required vapor boilup. This occurs because the concentration of reactant A on the lowest reactive tray
extra separation occurring with more stages concen- increases from 0.4425 to 0.5179 as NRX is changed from
trates the products in the reactive zone and shifts the 9 (the optimum) to 11. The concentration of product D
chemical equilibrium back toward the reactants on the at the same location decreases from 0.4817 to 0.4322.
lower and upper reactive stages. This effect was dis- Therefore, it takes more energy to keep component A
2504 Ind. Eng. Chem. Res., Vol. 43, No. 10, 2004
Figure 13. Effect of number of reactive stages for the base case
of (KEQ)366 ) 2 with constant number of separation stages NR )
NS ) 5.
Figure 14. Effects of pressure on the vapor boilup for three
different kinetic cases.
from leaving in the bottoms. Thus, there is an optimum
number of reactive trays for each pressure that mini-
mizes the vapor boilup, energy cost, and heat exchanger
cost.
The left graph of Figure 13 shows that there is a
minimum in the total annual cost curve at a certain
number of reactive trays because of the tradeoff between
increasing column cost and decreasing vapor boilup. For
this case, nine reactive trays are the optimum for all
pressures. This figure also indicates that the optimum
pressure is 8 bar for this specific case.
Figure 14 shows the effect of operation pressure on
vapor boilup. These results are for the three different
kinetic cases (KEQ)366 ) 1, 2, and 5 with the number of
reactive trays that is optimum for each case. The graph
shows that there is an optimum pressure for all three
cases that minimizes the vapor boilup. The higher
values of (KEQ)366 require lower vapor boilups and
operate at higher optimum column pressures. The
higher equilibrium constant pushes the reaction to the
right. The equilibrium constant decreases with increas-
ing temperature for an exothermic reaction. Therefore,
the column can operate at higher pressures when
(KEQ)366 is larger. It is possible to conclude from this
figure that the sensitivity to pressure increases as the
value of (KEQ)366 decreases. Therefore, operating at the
Figure 15. Economically optimum results for three different
kinetic cases.
optimum pressure is more important for small values
of (KEQ)366 than for large values. This figure shows that
the optimum pressures for (KEQ)366 ) 1, 2, and 5 are
6.5, 8.0, and 9.5 bar, respectively.
Figure 15 gives the economic optimum steady-state
design results for three different values of (KEQ)366. For
each case, the optimum pressure that minimizes the
vapor boilup is used, and the number of reactive trays
is varied over a range to find the minimum total annual
cost TAC. The upper graph shows that there is a
minimum in the TAC curve at some optimum number
of reactive stages. The optimum number of reactive
stages decreases with increasing values of (KEQ)366. The
column costs and total annual cost decrease as the value
of (KEQ)366 increases.
Results for five different kinetic cases are reported
in Table 6. The table includes the optimum design
parameters and costs in terms of the following optimi-
zation variables: (i) number of separation trays, (ii)
number of reactive trays, and (iii) the column pressure.
Also, the temperatures at the top and bottom of different
sections are included in this table.
Figure 16 shows the composition profile of the opti-
mum design for the base case of (KEQ)366 ) 2. The
highest composition of reactant A is at the bottom of
reactive zone where A is fed. The other reactant, B, has
its highest composition at the top of reactive zone, which
is also its feed tray. While the composition of A
decreases up through the reactive zone, the composition
of product C increases. The reverse occurs for reactant
B and product D through the reactive zone. The rest of
the column operates as a separation unit. Thus, the
composition of heavy product D increases down through
the stripping section, and the composition of light
product C increases up through the rectifying section.
Figure 17 shows the temperature profiles of the
optimum designs for the three different kinetic cases
(KEQ)366 ) 1, 2, and 5. The temperature profiles of the
three cases are similar, with higher temperatures for
higher values of (KEQ)366. Fairly significant temperature
breaks occur around tray 4 for all cases, and these tray
temperatures can be used in control schemes to infer
bottoms purity. A similar break occurs at different tray
numbers near the top of the column for each case. These
temperatures could be used to infer distillate purity. For
all kinetic cases, the temperatures show little change
in the reactive zone.
 Ind. Eng. Chem. Res., Vol. 43, No. 10, 2004 2505

Table 6. Optimization Results of Reactive Distillation Design

(KEQ)366
0.5 1.0 2.0 5.0 10.0 50.0
design variables
NR and NS 6 5 5 5 6 5
NRX 18 13 9 6 4 3
P (bar) 5.5 6.5 8.0 9.5 11.0 16.0
design temperatures (K)
base 415.8 423.1 432.8 441.0 449.0 467.6
bottom reactive 382.0 386.7 394.0 400.7 407.7 422.5
top reactive 365.1 383.3 393.9 402.6 409.7 428.4
reflux drum 341.5 346.6 353.2 358.9 363.8 377.3
design parameters
NT 30 23 19 16 16 13
VS (mol/s) 34.86 31.74 28.51 24.36 21.37 16.24
R (mol/s) 39.50 36.38 33.14 29.00 26.01 20.88
DC (m) 0.935 0.873 0.805 0.738 0.688 0.590
AR (m2) 51.28 46.68 41.93 35.83 31.44 23.89
AC (m2) 127.90 120.23 112.30 102.12 94.79 82.21
capital costs ($103)
heat exchanger 265.1 252.8 239.7 222.3 209.2 185.6
column 195.5 146.8 115.5 91.8 85.1 61.1
tray 6.2 4.3 3.1 2.3 2.1 1.3
energy cost ($103/year) 150.2 136.8 122.8 105.0 92.1 70.0
TAC ($103/year) 305.9 271.4 242.3 210.5 190.9 152.7

Figure 16. Composition profile of the optimum design for the Figure 18. Effect of conversion for the base case of (KEQ)366 )
base case of (KEQ)366 ) 2.0. 2.0.

at each pressure are given for base kinetic case of

Figure 17. Temperature profiles of optimum designs for different
kinetic cases.
Figure 18 illustrates the effect of the conversion on
the total annual cost for different pressures. The
conversion is increased to 99%, and the optimal results
(KEQ)366 ) 2. To achieve the required purity, the
optimum number of separation stages is NS ) NR ) 7
for this case, which is 2 more than in the 95% conversion
system. The optimum number of reactive stages is 13,
which is 4 more than in the base case. The optimum
pressure is the same (8 bar) as in the 95% conversion
case. These results indicate that the TAC of the system
increases when a higher conversion is required.
6.3. Comparisons. Comparisons of conventional
reactor/separator/recycle and reactive column design
configurations at their economically optimum steady-
state designs are presented in Table 7 for five different
kinetic cases.
The results indicate that the TACs of both design
configurations decrease as the value of (KEQ)366 in-
creases. The results also show that the reactive distil-
lation column configuration has lower capital and
energy costs than the conventional configuration for all
kinetic cases. These costs result in lower TACs for the
reactive distillation columns compared to the reactor/
column/recycle systems.
2506 Ind. Eng. Chem. Res., Vol. 43, No. 10, 2004
Table 7. Economic Comparison of Two Different Process
Flowsheets
(KEQ)366
0.5 1.0 2.0 5.0 10.0 50.0
capital cost ($103)
conventional 1291.5 1116.8 984.0 861.6 773.6 612.6
reactive column 466.8 403.9 358.4 316.4 296.4 248.1
3
energy cost ($10 /year)
conventional 502.9 425.4 361.9 292.8 256.3 195.7
reactive column 150.2 136.8 122.8 105.0 92.1 70.0
TAC ($103/year)
conventional 933.4 797.7 689.9 580.0 514.2 399.9
reactive column 305.9 271.4 242.3 210.5 190.9 152.7
7. Conclusion
The economically optimum steady-state designs of a
multiunit reactor/column/recycle process and a reactive
distillation column are compared for different values of
chemical equilibrium constants. Identical production
targets and prices are used. Three optimization vari-
ables are used to find the optimal results for the two
systems. The conventional system has the reactor
holdup, the reactor temperature, and the composition
of reactant B in the reactor as optimization variables,
whereas the reactive column configuration has the
number of separation stages, the number of reactive
stages, and the column pressure as optimization vari-
ables.
As (KEQ)366 becomes larger, the capital cost and the
energy cost decrease for both configurations. These
decreases result in a decrease of the TAC for both
systems. When compared for different kinetic cases,
reactive distillation columns have lower TACs than
reactor/column/recycle systems for all values of (KEQ)366.
Thus, eliminating a reactor and a column with heat
exchangers reduces costs by a factor of 2-3.
Ideal phase equilibrium is assumed in this study so
that a clean comparison can be made and the system-
specific complexities of azeotropes do not cloud the
fundamental issues. The results of this study should
provide some general insights and guidance related to
the differences between the two alternative flowsheets
that arise because of fundamental structural differences
and limitations.
In this study, we assume that relative volatilities are
constant and fairly large (R ) 2). Studies are underway
to explore the effects of changes in the relative volatili-
ties on the two flowsheets. Two types of changes will
be considered: (1) The relative volatilities between
adjacent products and reactants (RCA and RBD) will be
reduced. We expect that this will increase the energy
requirements in both flowsheets and increase the num-
ber of trays in the distillation columns of the conven-
tional flowsheet and the number of stripping and
rectifying trays in the reactive distillation column. There
will probably be little impact on the optimum reactor
temperature in the conventional process. There should
be little effect on the optimum pressure of the reactive
distillation column. However, the number of reactive
stages might change. (2) The relative volatilities will
be made temperature-dependent (decreasing with in-
creasing temperature). This should emphasize the im-
portant difference between the two processes. Specifi-
cally, in the conventional flowsheet, the reactor and
column can operate at different pressures. This is not
true in reactive distillation.
Future work will also compare the dynamics and
controllabilities of the two systems.
Nomenclature
aF ) preexponential factor for the forward reaction
(kmol‚s-1‚kmol-1)
aR ) preexponential factor for the reverse reaction
(kmol‚s-1‚kmol-1)
AC ) heat exchanger area for the condenser (m2)
AR ) heat exchanger area for the reboiler (m2)
B ) bottoms flow rate in the column (mol/s)
D ) distillate flow rate in the column (mol/s)
DC ) diameter of the column (m)
DR ) diameter of the reactor (m)
EF ) activation energy of the forward reaction (cal/mol)
ER ) activation energy of the reverse reaction (cal/mol)
F ) effluent flow rate from the reactor (mol/s)
Fi ) feed flow rate on tray i (mol/s)
F0j ) fresh feed flow rate of reactant j (mol/s)
kF ) specific reaction rate of the forward reaction
(kmol‚s-1‚kmol-1)
kR ) specific reaction rate of the reverse reaction
(kmol‚s-1‚kmol-1)
KEQ ) equilibrium constant
LC ) length of the column (m)
Li ) liquid flow rate from tray i (mol/s)
LR ) length of the reactor (m)
LR ) liquid flow rate in the rectifying section (mol/s)
MB ) liquid holdup in the column base (mol)
MD ) liquid holdup in the reflux drum (mol)
Mi ) liquid holdup on tray i (mol)
Mw ) molecular weight of all species in the mixture
(g/mol)
NF ) feed tray in the column
NR ) number of rectifying trays
NRX ) number of reactive trays
NS ) number of stripping trays
NT ) number of trays in the column
NTmin ) minimum number of trays in the column
P ) column pressure (bar)
S
Pi,j ) vapor pressure of component j on tray i (bar)
R ) ideal-gas-law constant (cal‚mol-1‚K-1)
Rj ) rate of reaction for component j (mol/s)
RR ) reflux ratio in the column
RRmin ) minimum reflux ratio in the column
Ti ) column temperature on tray i (K)
TR ) temperature of the reactor (K)
UC ) overall heat-transfer coefficient in the condenser
(kJ‚s-1‚K-1‚m-2)
UR ) overall heat-transfer coefficient in the reboiler
(kJ‚s-1‚K-1‚m-2)
Vi ) vapor flow rate from tray i (mol/s)
VNT ) molar flow rate from the top of the column (mol/s)
VR ) molar holdup of the reactor (mol)
VS ) vapor boilup (mol/s)
xB,j ) bottoms liquid composition of component j
xD,j ) distillate liquid composition of component j
xi,j ) liquid composition of component j on tray i
yB,j ) bottoms vapor composition of component j
yi,j ) vapor composition of component j on tray i
zj ) mole fraction of component j in the reactor
zi,j ) mole fraction of component j in feed tray i
Greek Symbols
Rj ) relative volatility of component j
βpay ) payback period (year)
∆HV ) average heat of vaporization (cal/mol)
∆TC ) temperature difference in the condenser (K)
∆TR ) temperature difference in the reboiler (K)
λ ) average heat of reaction (cal/mol)
νj ) stoichiometric coefficient of component j
χ ) conversion

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Received for review November 13, 2003
Revised manuscript received February 25, 2004
Accepted March 5, 2004
IE030832G