Chcmicol Engineering Scirnee, Vol. 46, No.

516, pp
Printed
in Great Britain

1361-1383,

1991.

oab9 2509/91
s3.m
+ 0.00
1991 Pergamon
Press plc
0

SYNTHESIS
OF ISOTHERMAL
REACTOR-SEPARATOR-RECYCLE
SYSTEMS
ANTONIS
Department

C. KOKOSSIS

of Chemical
(First

Engineering,

received

12 March

and

A. FLOUDAS+

CHRISTODOULOS

Princeton

University,

1990; accepted

Princeton,

in revised firm

NJ 085444263,

31 July

U.S.A.

1990)

Abstract-A
systematic synthesis approach
is presented for isothermal
reactor-separator-recycle
systems.
The approach
proposes a general superstructure
of different reactors and separation
tasks and features all
the potential interconnections
among the proposed units. The synthesis problem based upon the proposed
superstructure
results in a mixed integer nonlinear
programming
(MINLP)
formulation
in which the
objective function involves both integer and continuous
variables and is subject to a nonlinear
set of
constraints.
A variety of objectives was selected for the synthesis problem such as the minimization
of the
of its profit, as well as objectives traditionally
used for
total annual cost of the plant and the maximization
optimizing the performance
of a reactor network such as the product yield and selectivity. Discussion of the
results and comparison
among the different solutions obtained provided the ground for conclusions related
to the potential trade-offs and the performance of the isothermal chemical systems under consideration.

1. INTRODUCTiON

most chemical processes reactors are sequenced by

systems that separate the desired products out of their
outlet
reactor
streams and recycle the unconverted
reactants back to the reactor system. Despite the fact
that process synthesis has been developed into a very
active research area for the last two decades, very few
systematic procedures
have been proposed
for the
synthesis of reactor-separator-recycle
systems. The
proposed evolutionary
approaches are always based
upon a large number of heuristic rules to eliminate the
wide variety of choices. Many of these heuristics are
actually extensions of results obtained by separately
studying the synthesis problem of reactor networks or
separator systems and, therefore, the potential tradeOITS resulting
from the coupling
of the reactors
with
the separators have not been investigated.
The delay in the development of a general synthesis
strategy
that will set the basis for a rigorous and
systematic
search for the optimal
reactor-separator-recycle
configuration
is mainly due to the difficulties arising from the large number of structural
alternatives and the nonlinear design equations of the
participating units. Instead of focusing on an optimal
search procedure, the various proposed methods have
restricted the synthesis problem into a limited search
around a feasible operation point. Thus, although it is
often possible to identify directions of potential improvements, the finally obtained solution can never be
claimed, structurally and/or operationally, to be even
a local optimal point.
In the optimization
of reactor-separator-recycle
systems a very limited number of publications exist.
Conti and Paterson (1985) proposed a heuristic evolutionary technique to solve the synthesis problem. First
a hierarchy of heuristics is adopted that target to: (i)
minimize process complexity,
(ii) maximize process
In

Author
CES

*6-5/6-K

to whom

correspondence

should be addressed.
1361

yield, and (iii) select the distillation column which

minimizes total heat load. According to the proposed
hierarchy a base case design is quickly established
where everything is specified. Incremental changes are
then introduced to the system by successively relaxing
the heuristics so that a low cost process topology
is
obtained at each stage. It is evident that since there is
no unique way of relaxing any of the above heuristics,
arbitrary decisions should often be made to provide
directions of potential changes in the system. Performing a case study for the Van der Vusse reaction,
the authors
were able to compare their results with
reported optimal solutions for the isolated reactor
system. The comparison
made clear that a design
based upon the maximization of reactor yield is much
inferior to the design based upon the integrated flow
sheet.
Floquet el ul. (1985a, b) proposed a tree searching
algorithm (a branch and bound method) in order to
synthesize
chemical
processes
involving
reactorseparator-recycle
systems interlinked
with recycle
streams. The reactor network of this approach
is
restricted to a single isothermal CSTR or PFR unit
and the separation units are considered to be simple
distillation columns. The conversion of reactants into
products
and the temperature
of the reactor, as well as
the reflux ratio of the distillation
columns, were
treated as parameters. Once the values of the parameters have been specified, the composition
of the
outlet stream of the reactor can be estimated and
application
of the tree searching algorithm on the
alternative separation tasks provides the less costly
distillation
sequence. The problem is solved for several values of the parameters and conclusions
are
drawn for different regions of operation.
Pibouleau
et al. (1988) provided a more flexible
representation for the synthesis problem by replacing
the single reactor unit by a cascade of CSTRs. They
also introduced parameters for defining the recovery
rates of intermediate components into the distillate,

1362

ANTONIS

C. KOKOSSIS

and

the split fractions of top and bottom components that

are recycled toward the reactor sequence, as well as
parameters for the split fractions of the reactor outlet
streams. A benzene chlorination process was studied
as an example problem for this synthesis approach. In
this example, the number of CSTRs in the cascade was
treated as a parameter that ranged from one up to a
maximum of four reactors. By repeatedly solving the
synthesis problem an optimum number of CSTRs was
determined.
In this paper a general approach based upon mathematical programming
techniques is proposed for the
synthesis of reactor-separator-recycle
systems. A
superstructure is postulated with all the different alternatives for the reactor and separator network, as
well as for their possible interconnections.
Different
separation tasks, different types of reactors, different
reactor configurations and different feeding, recycling
and bypassing strategies are considered. The synthesis
problem is formulated as a mixed integer nonlinear
programming
problem
(MINLP).
The continuous
variables include the stream flow rates and compositions of the reactors and separators while the integer
variables describe the existence of the reactors and the
distillation
columns. The solution of the (MINLP)
formulation will provide an optima1 configuration of
the reactor-separator-recycle
system.

2.

PROBLEM

STATEMENT

For a chemical process in which a reactor network

with a reaction system of known kinetics is followed
by a sequence of separation tasks that are required to
extract the desired products and recycle the unconverted reactants, the synthesis problem consists of
systematically determining the reactor-separator-recycle system that operates so that a given performance
criterion (e.g. total cost or profit of the plant, yield or
selectivity
of desired products,
conversion
of reactants) is optimized. The solution of such a problem
should provide information about:
(a) the reactor network (types and sizes of reactors,
feeding strategy and interconnections
among the
reactors);
(b) the separator network (appropriate separation sequence and sizes of separators);
(c) the interconnection
between the two networks via
the allocations
of the outlet streams from the
reactors and the allocations of the recycles from
the separators back to the reactors.
In the proposed synthesis problem
sumptions are made.

the following

as-

(1) All separators are considered to be distillation

columns while the available reactor units consist
of continuous stirred tank reactors and plug flow
reactors that are approximated
by equal volume
CSTRs (SCs). In the separation level, distillation
was assumed to be the only method available,

CHRISTODOLJLOS

A.

FLOLJDAS

although, as will become clear in the following

sections. alternative separation methods can also
be handled in a way similar to distillation.
(2) All distillation columns are simple (i.e. one feed
and two products) and operate as sharp splits of
the light and heavy key components.
No distribution of components
is allowed in both the
distillate and bottom products and configurations
that include nonsharp separators, like those described by Aggarwal and Floudas (19901, are not
considered.
(3) The thermodynamic
state of the various streams
in both the reactor and separation networks are
supposed to be known. For the examples presented in this paper, the feed streams of all
columns are saturated liquids at the pressure of
the column. Distillate and bottom streams are
also considered to be saturated liquids at their
bubble points.
(4) The operating
conditions
of the various units
(pressure, temperature, reflux ratio of the columns)
are not considered as optimization
variables and
are fixed at nominal values. The heating and
cooling requirements are directly provided by hot
and cold utilities and, therefore, no heat integration takes place.
Assumption (1) does not impose any restrictions on
the potential of the proposed reactor network. Due to
the fact that CSTRs and PFRs represent the two
extreme types of reactor performance, superstructures
of these units are capable of handling simple and
complex types of reaction mechanisms since they can
approximate
reactors with various degrees of mixing
and can provide for different feeding, recycling and
bypassing strategies (Kokossis
and Floudas,
1989,
1990). Furthermore, batch and semi-batch processes
can also be studied from their space equivalent plug
flow reactors.
Assumption (2) can be justified for a large number
of chemical processes where product specifications
require very pure products and high recoveries only
should be considered. Although assumption (3) is a
useful postulation that enables the effective formulation of the synthesis problem, assumption (4) should
be considered as the most restrictive assumption of
the approach.
This is not only because nonisothermally operated units that are excluded according
to this assumption
may appear more profitable
choices for the synthesis problem, but also because the
potential heat integration among the hot and cold
streams of the reactor-separator-recycle
system is
always expected to reduce the energy requirements for
the plant and result in a much less costly alternative
solution. The nonisothermal
operation and the heat
integration
issue will be addressed
in a future
publication.
3. THE

SYNTHESIS

APPROACH

Based upon the set of assumptions introduced in

the previous section, it is intended to present a sys-

1363

Synthesis of isothermal reactor-separator-recycle systems

tematic strategy potent to handle the isothermal synthesis problem of reactor-separator-recycle
systems.
The basic parts that constitute the proposed approach
consist of the following.
3.1. Derivation of cost models via simulation data
The synthesis problem involves cost expressions of
the various units. Since the specifications of the feed
streams of the columns are variables in this approach,
a series of simulations is performed by slightly relaxing the split assumption in order to provide cost data
for different feed flow rates and compositions.
Subsequent regression analysis of these data determines
the expressions for the cost of each column as a
function of these variables.

3.2. Generation of the superstructure

The basic idea behind the generation of the superstructure is to include all different configurations for
the reactor-separator-recycle
system. In the reactor
network, the superstructure should feature aIternatives for reactors in series, reactors in parallel or
series-parallel,
reactors with multiple feeds and recycles, as well as bypasses around the reactor units.
The superstructure should account for all the potential interconnections between the reactor network and
the separator network, it should include all potential
allocations of the recycle streams originated from the
separators and leading to the reactor units, and, in the
separation level, it should include all the alternative
separation sequences.

3.3. Formulation of the synthesis problem

Based upon the proposed superstructure, the synthesis problem is formulated as a constrained optimization problem. Continuous, as well as integer, variables are introduced. The integer variables represent
the existence of each particular reactor and separator
unit; these variables are assigned a nonzero value if
the associated unit exists in the solution and a zero
value otherwise. The continuous variables consist of
the flow rates and compositions
of all streams, the
volumes of the reactors, the operation time of the
plant, and the costs associated with each unit. The
objective function is generally a mixed integer nonlinear function which is subject to a nonlinear set of
constraints defined by the mass balances around the
various splitters and mixers of the superstructure, the
mass balances around the reactors and separators,
and the logical constraints.

3.4. The proposed solution algorithm

The above mathematical formulation
results in a
nonlinear
programming
problem
mixed
integer
(MINLP),
the solution of which is obtained by decomposition
and iteration according
to the generalized Benders decomposition
algorithm (Geoffrion,

1972). According to the specified criterion (e.g. profit

or venture cost, yield or selectivity of the product), the
solution will provide information about an optimum
structure of the reactor-separator-recycle
system, as
well as information about the flow rates and composition of the various streams and the sizes of the reactor
and distillation units.

4. COST

MODELS

AND

SIMULATION

DATA

The formulation of the synthesis problem involves

expressions for the capital and operating cost of the
reactors and the distillation columns. Although for
the reactor units such expressions are readily available, for the distillation columns additional effort is
rate
required. This is due to the fact that the feedfiow
and composition
of each column
are considered
as
optimization
variables in the synthesis problem. The
cost of a column is clearly a function of these variables
and, since the function itself is not known, it has to be
extracted from a series of simulation data obtained for
a range of these variables.
Guthries cost module (1969) summarizes the data
necessary for estimating the cost of a column to be: (i)
the shell size and material,
(ii) the pressure of the
column, (iii) the number, diameter and type of trays,
and (iv) the heat duties of the reboiler and condenser.
The tray sizing can be based on some reasonable
values of the flooding factor. A value of 78% is used
for columns with diameters greater than 1.2 m and
75% for columns with smaller diameters. Valve trays
were used in all cases. The shell size and the material
can generally be prespecified and the pressure of the
columns has already been assumed to be known. With
the economically
optimal reflux ratio being 1.2 times
the minimum (King, 1971), shortcut distillation calculatious were performed for a wide range of feed flow
rates and compositions
and provided the number of
trays and the heat duties for the condenser and reboiler. Fixing the number of trays to the number
calculated by the shortcut distillations, a second series
of rigorous calculations provided additional information about the diameter of the trays. In this work, all
the simulation
data
was
obtained
using
the
PROCESS
flow sheeting system (Simulation Sciences,
1985).
Once the number of trays, the size of trays and the
heat duties of the reboiler and the condenser have
been calculated, the data necessary for estimating the
cost of the columns have been obtained. Mathematical expressions are next derived that provide the cost
of a column as a function of its feed flow rate and
composition. This is achieved by fitting various models to the simulation data and using regression analysis via SAS (Statistics Analysis Software). The capital cost Cosr:lp and the operating cost Cost::
of each
column were expressed in terms of the compositions
of the feed components of the column XFC,+_,
(kth
degree polynomial), as well as the feed Aow rate of the
columns FC,,,. The cost expressions are in the general

ANTONIS

1344

C. KOKOSSIS

and

form:

+a clo,.mXFCm...,

. . . + &mXFC&

+b hnX~Cm,w~

. .

+ bL,m XFCk,,,

(11
>

G-9
>

where h,
d,..,,
&.,,,
. - , 4,,col, bLOl. b,l col, . . . ,
bkm co, are constants available from the regression analysis for each column and Msd
is the set of feed
components of the column. The above expressions for
the costs are nonlinear in both the feed flow rates and
the compositions
of the considered components. The
cost dependence
on the composition
vector is expressed via a polynomial
form that features positive
and negative coefficients while the dependence on the
flow rate is expressed in a bilinear form that includes
the polynomial of the composition vector and the feed
flow rate. The exact type of the nonlinearities, however, is dependent on the problem under consideration and the fitting expressions resulting from the
regression analysis.
The capital cost Cmt,,,,Cap of the reactors is assumed
to be a linear expression of the reactor volume in the
form:
COStCaP
relf -- Y,,.. + La,

vi

(3)

are respectively the fixed charge

where Y,,,, and L,
and variable charge investment cost of the reactor and
V Tea=is the reactor volume. In all cases, the operating
cost of the reactors is assumed to be negligible.
5. THE

GENERATION

OF

THE

SUPERSTRUCTURE

A reactor-separator-recycle
system consists of two
different networks: the reactor network and the separator network. The reactor network consists of the
reactor units and the interconnecting
streams associated with these units while the separator network
consists of the different separation tasks that constitute the desired
separation
process.
A reactorseparator-recycle
superstructure
should
generally
provide options for all the structural alternatives for
the units (reactors, separators), as well as a complete
stream network that will allow for all the different
interconnections
among them. At the reactor network
level, the superstructure should feature all the possible
arrangements
of the reactors and should consider
cases of different types of reactors with multiple feeds,
recycles and bypasses, as in Kokossis and Floudas
(1989, 1990), as well as different allocations for the
recycled reactants that flow purified as bottom or
distillate streams out of the separators. In the separation level, the superstructure should include all different separation sequences and all different interconnections among the separators and the reactors. It should

CHRISTOD~ULOS

A.

FLOUDAS

be noted that the specifics of a system may provide

additional alternatives that cannot be included in a
general purpose superstructure. These cases are not
addressed by the present approach which intends to
handle
the synthesis
problem
of reactor-separator-recycle
systems in a general form. Once the
mechanism is known, however, the extension of the
superstructure in order to accommodate
special features is always possible.
The proposed superstructure is best described by
defining a basic set of mixers and splitters associated
with the various units. These include the set of mixers
MX:,,
prior to each i,, CSTR, mixers MXSCi,,
sk
prior to each sk SC-unit of the i,, PFR, mix&s
MXRC,
associated with each recycled component rc,
mixers MXSS,,
prior to each separation sequence sq,
splitters SL$ associated with each feed stream of mf
component
and splitters SLP in the outlet of each
reactor i.
The
superstructure
of the reactor-separatorrecycle system is then generated so that:
(1) streams originated from any of the SL$-, MXRC,,
and SLp lead to any of the mixers MXiB
and
MXSC! z,=,=.sk;
(2) streams originated from any of the SLput lead to
any of the mixers MXSS,;
(3) streams originated from each MXSS,,
lead to each
one of the mixers MXRC,,;
the MXSCi,,.,,,
and the
(4) outiets of the MXF,,,
MXSS,
feed the CSTRs, the SCs and the leading
separator of the sq separation sequence respectively;
(5) splitters SLP are fed by the outlets of the reactors
and mixers MXRC,,
(apart from MXSS,,)
by these
streams of the separators that produce pure rc.
In order to illustrate examples of superstructures
generated according to the above propositions,
the
examples of two different reaction mechanisms are
considered. In the first example the reactor network
consists of three CSTRs and the components to be
separated are A, B and C with their relative volatility
in this order. The consecutive reaction mechanism
kl
kl
n-EC is assumed to take place with B
denoting the desired product and A the fresh feed
component. The potential separation tasks are A/EC,
AS/C, B/C and A/B. The component which should be
considered For recycling is A and flows as distillate
from columns A/BC and A/B. The generated superstructure, shown in Fig. 1, features all the possible
interconnections
among the reactor units (streams 7,
8, 10, 11, 15 and 16), among the reactor and the
separation units (streams, 5, 6, 12, 13, 17 and 18), and
all the potential recycles from the separation network
to the reactors (streams 25, 26 and 27).
The
different
configurations
for the reactorseparator-recycle
system can be obtained by eliminating the appropriate streams of the proposed superstructure. Thus, elimination of all but streams 1, 7, 11,
14, 18, 22, 24 and 27 results in the configuration

Synthesis

of isothermal

reactor-sepaiator-recycle

systems

1365

1366

ANT~NIS C. KOKOSSIS

and CHRISTODOULOS

shown in Fig. 2(a) where the three CSTRs are connected in series, the separator system includes
columns A/BC and B/C and a total recycle of A is fed
into the first CSTR. Should all but streams 1, 2,3,4, 5,
9, 12, 14, 17, 21, 23 and 26 be eliminated from the
superstructure, the configuration of Fig. 2(b) is obtained where the CSTRs are connected in parallel, the
separator network consists of columns AB/C and A/B
and the recycle stream from A/B feeds the second
CSTR. A different configuration, illustrated in Fig.
2(c), is the case where streams 1, 2, 8, 9, 14, 17, 12, 21,
23, 25 and 27 only are activated. In the reactor
network, the first and third CSTRs are connected in
series and the second reactor is in parallel with the
serial arrangement of the other two CSTRs. The
separator system consists of columns AB/C and A/B,
while the recycle of A is fed into the first and third
CSTRs.
As a final example, the reactor-separator-recycle configuration of Fig. 2(d) is shown. The
configuration results by considering only streams 1, 7,
9, 12, 14, 17, 21,23, 25 and 27 from the superstructure
of Fig. 1 and consists of reactors CSTR- 1 and CSTR-2
in series with CSTR-2 feeding column A/BC, the
distillate of which feeds CSTR-3 and CSTR-1.
In case the reactor network consists of two CSTRs
and one PFR and the assumed reaction mechanism is
B 2 C the generated reactorof the form: As
separator-recycle superstructure is shown in Fig. 3.
As in the previous example, B is assumed to be the
desired product while C is a byproduct, the recycling
of which may or may not be desirable. Thus, the
superstructure features the potential recycle streams
25, 26, 27, 32, 33 and 34 which lead toward CSTR-2,
CSTR-1
and PFR-1. According to the proposed
features for the plug flow reactor, each potential feed
stream of the PFR (1,4, 10, 15,27 and 34) is split into a
number of substreams equal to the number of the
SCSTRs in the PFR representation. As a result, different feeding strategies can be obtained for the PFR
unit as illustrated in the configurations
shown
in
Fig. 4.
In Fig. 4(a), the reactor network
consists
of the
CSTR-1
in series with the PFR, the inlet stream of

is unevenly distributed along the reactor.-The

separator system consists of columns A/BC and B/C
and A is the only recycled component. In Fig. 4(b), the
reactor network is restricted to the plug flow reactor,
columns AB/C and A/B constitute the separator system and components A and C are both recycled
toward the PFR. A total recycle of A is fed in the front
section of the PFR while a substream of the produced
C is fed in the middle and ending section of the
reactor. In the final example,
shown in Fig. 4(c), the
reactor network consists of all three reactors. The
leading PFR unit is fed by fresh and recycled reactant
A and is connected in series with a parallel arrangement of the two CSTRs. The separator system consists of columns A/BC and B/C. The recycled component A is feeding the PFR while the recycled component C is feeding the CSTRs.
which

4.

VARIABLES

A. FLOUDAS
AND

PARAMETERS

OF

THE

SYNTHESIS

PROBLEM

The basic index sets used to define the variables and

parameters of the synthesis problem include the set of
components M = {ml, the set of reactors Z = (i}, the
set of the columns L = (I} and the set of intermediates
N = { nJ. The latter set consists of all groups of two or
more components discharged in the same outlet
stream of a separator.
A number of subsets of these sets are also introduced and include:
Subsets of M
{m/me M is a recycled component}
{mlmt M is a fresh feed component)
{m/me M is a desired product]
{ mlm E M participating
in rp E RP path kinetic expression}
Mfeed
1

_
-

Mbot
1

Mdis
I

_
-

{mlmE M is a feed component of column

IEL)
{m/me M is a bottom component of column
IEL)
of
{rnlrn~ M is a distillate component
column I E L}

Subsets of Z
ZcSrR = { ili~Z is a continuous stirred tank reactor}
ZPFR= {iii E Z is a pIug flow reactor}
Subsets of L
J = { I[! E L is a leading column}
L!F:d = {l/f EL with feed the intermediate
n E IV)
L.tz = {ZIIE L with bottom
the intermediate
n E N}
I$: = (I//E L with distillate the intermediate n E N)
L1.E = (ZIIEL
produces
recycled
component
mEM)
L;tm= {ZllsL
produces desired mcMdp).
In addition to the above sets, there is also the set of
the reaction paths RP = {rp} and the set SK = (sk} of
the subunits (CSTRs) that represent each individual
plug flow reactor.
The variables of the synthesis problem are defined
over the above sets and subsets and consist of continuous and integer variables. The first set of continuous variables includes variables associated with
the cost or the profit of the plant,

CO&: annualized cost of the plant

Pro$r: annualized profit of the plant,
as well as variables associated with the cost of the
various units and the operation time of the plant,
CustFap:capital cost of
Co@?
capital cost of
CostFper: operating cost
8: total operation time

column 1
reactor i
of column

of the plant.

Another set of variables is related to the flow rates

of the streams that constitute the proposed super-

Synthesis of isothermal

reactor-separator-recycle

1367

systems

9
f

II
B

-l!I!b!

Eel--h
C

(a)

C
L-J
4

B
c----

CSTR

CSTR-2

- 3

(d)
Fig. 2. Reactor-separator-recycle

configurations

obtained from the superstructure of Fig. 1

I-

28

26

:41
5L
22

24

Fig. 3. Reactor-separator-recyclesuperstructureconsistingof one CSTRand one PFR and separating three components.

Synthesis of isothermal reactor-separa(or-recycle systems

1369

(b)

Fig. 4. Reactor-separator-recycle
structure
flowrates,

and

consist

of

the

fresh

configurations obtained from the superstructure of Fig. 3.

feed

stream

FD,:

total fresh feed stream of component m E M mJ

fresh feed of reactant m E M w in reactor i
sk substream of FR,.,
(i E IPFR, sk E SK),
FRSw>,:
FRi,m:

streams leading to or originated

(CSTRs and SCs),

from the reactor units

IN,: inlet stream of reactor i

OUT,: outlet stream of reactor i
TNSi,,k: inlet stream of sk SCSTR
(i.zlPFR, skESK)
OUTSi,sk:
outlet stream
(i E IPFR, sk E SK)
BP+:

bypass

around

of sk SCSTR

sk SCSTR

FC,: total feed of column I

B,: bottom product of column I
D,: distillate product of column 1,

as well as streams that interconnect different units of

the superstructure such as the streams among the
reactors,
interconnecting
stream from reactor i to
reactor k; i, ke1
sk substream
of RR,_, (itz I, k E IPFR,
RRSi.r,,r:

RR,.,:

Sk E SK)
of

reactor

of reactor

of

reactor

(i E IPFR, sk E SK),
streams leading to or originated from the separator
units (feed, bottom and distillate streams of the distillation columns),

i
i

or streams connecting the reactor

separator system and vice versa,

network

to the

MM,.,: reactor network recycle in front of column 1

merging with REC,
(1 E J, m E M)
RMi,I: stream from reactor i to leading column 1E J
MRSi,,.Sk 1sk substream of MRi,,, (i E I PER, m E M 111,
sk E SK)
recycle
MRi,m:

reactor i

stream

of component

rnE M

to

ANTONIS

1370

C. KOKOSSIS

and

REC,:
total recycle of pure m (me M)
PG,:
total purge stream of m (m~A4~).

A. FLOUDAS

CHRISTODOULOS

a: payout

Figure
5 shows
the reactor-separator-recycle
superstructure (one PFR, one CSTR and a threecomponent separation process) along with the stream
variables that have been introduced above. A different
set of variables is associated with the reaction rates
and the volumes of the reaction units,
R,,.i: reaction rate of reaction rp in reactor i
R&i,& reaction rate of reaction path rp in sk
SCSTR of reactor c (iEIPFR)
V,: volume of reactor i
of reactor i (if IPFR,
vSi.J* ; volume of sk SCSTR
Sk E SK),
as well as the concentrations of the species that appear
in the reaction rate expressions,
CNi,,:
concentration of component m in the output
of reactor i
of component
m in
CNSi,sk,m: concentration
0 U TSi,,r.
A final set of continuous
variables considers the
molar fractions of all the streams of the superstructure
and consists of:

molar fraction of component m in FC,

molar fraction of component m in BI
XD,,,: molar fraction of component m in D,
molar fraction
of component
m
XMKwsw:

time
p: income tax rate
SP,: sales price of component m
PR,:
minimum production of desired m E Mdp,

as well as the chemical process (reaction mechanism,

reaction mixture) and the plug flow reactor representation (maximum allowable SC units),
Y,~,,: stoichiometric coefficient of component
reaction path rp
N,,: number of SK elements
k,: reaction constant for reaction path rp
MVm: molar volume of m.

7. FORMULATION

:.{z#

XFC,,,:

costann = in

molar fraction of component m in INi

molar fraction of component
m in
XOuTi,,k3,:
OUT,

XOUTS,,,:

molar

fraction

of

component

m in

molar

fraction

of

component

in

OUTSi,,*.

Apart from the continuous variables, the proposed

formulation
also includes integer variables that describe the structural alternatives
of the reactorseparator-recycle
system. The set of integer variables
includes:
Zi: binary variables associated with reactor i
Y,: binary variable associated with column 1
associated with sk SCSTR
zsi,sli
: binary variable
reactor i (i E IPPR).

CostfP +

c
&I.

COStfaP

1
(4)

MRi,,r
XIN,,,:

INS+

PROBLEM

7.1. Objective function(s): the difSerent cases

The different objectives that have been considered
in this approach include those related to the economics of the nlant. like the profit and the annualized
venture cost df the system, *and those related to the
efficient utilization of the reactants like the overail
yield and selectivity.
The exDression for the annualized venture cost of the
plant is of the general form:

XB,,,:

XINSi,sk,nt:

OF THE SYNTHESIS

m in

of

The above binary variables represent the existence

or not of each unit. Thus, if the reactor i (column
r)
participates in the superstructure, then Zi ( Yr) takes
the value of 1. Otherwise it takes the value of 0. The
introduction of the binary variables ZSiVslrrin addition
to Zi, reflects the alternative of having activated only
a subset of the available SCSTRs given by N,,.
Besides the continuous and integer variables of the
problem, a set of parameters is introduced which is
related to the costing and the specifications for the
plant,

where
Costa = the
Cosp
= the
Costpap = the
Cosf;lper = the

annual venture cost of the plant

total capital cost of reactor unit i
total capital cost of column I
annual operating cost of column 1.

In Section 4 it was shown how to derive the capital

and operating costs of the units. In the case where a
particular unit does not participate in the solution the
cost associated with the unit should be eliminated.
Logical constraints that are introduced later in this
section force the feed flow rates and the volumes of
nonexisting reactors and coIumns to take zero values,
thus eliminating the operating costs of the units and
their variable charge investment costs. For the fixed
charge investment costs also to be eliminated in the
case where the unit does not exist, the expressions for
the capital costs are written in the equivalent form:

Costpa~

yiz, + 6, v,.

For the total profit of the plant the expression

(6)
used

Synthesis

of isothermal

reactorseparator-recycle
A

systems

1371

1372

ANTONIS

C.Ko~ossrs

and CHRISTODOULOS

A. FLOUDA~

1 < sk < N,,,

ipEIPFA,

is:
Pro&

SP,

13. FC,,,

[EIf,-; ?nehfLp

,s;

/SP,

0. FD,

INi,

. XFC,,,
Cost

(i) molar balances for the feed stream splitters, and

PFR stream splitters
FD,

FL

RR,,,

CFR~,~
i.zr

= 0

mEMmf

(8)

c
FRSis,k,,
skcSK

= 0

iE IPFR, mEMm/

(9)

RRSi,;p,,t

= 0

iE I, ipe ZPFR

(10)

= 0

iEZPFR, rnE Mm

(11)

sk&K

MRi,m

MRSi,,,,k

sk&K

(ii) molar balances for the mixers in the inlet of each

CSTR unit

c RRSi,ip.sk . XOUT,.,
iEI

+ m,&_~MRSip,m,.,k

- INSip,sk+ I

i E ZCsTR,

(iii) molar
unit

sk =

(iv) moIar balances

each reactor

Bpip,sk - 1

c RR,,, . XOUT,,,

OUTSip,sk-

OUT,-

BPip.slr. XINS+,,,
OUT,;

for the mixers

sk = NsK,

XINSip,s~.rn = 0

(15)

meM

QxIPFR,

skESK,

me M

(16)

column
c RM,,I.

XOUT,,,

(vi) molar
structure
REG,

1
MM,,,
rn.z&frc

FC, . XFCI,,

balances

REC,

PG,

mEM

(17)

. XFC,sm

Id

IEJ,

mixers of the super-

for recycle

1 MM,,,,

. XFC,,,

= 0

-~MR,,,;XMR,=,=O

mEM,mrEM

c
XFC,,,
,ELiZ

. FCI = 0

(18)

mr

EMC
(19)

(vii)

summation

of the volumes
C

of the SC units

VSi,sk = 0

ifz ZPFR

of the mole fractions

c XMR,,,,
m

prior to each SC

XIZVi_-

msA4
1.m

INS+

iEI,

= 0

+ OUTSip.slr . XOWTSip.sk,m

(20)

of the streams

1 =O

mrEMrC

(21)

1=0

iEI

(22)

c XOUTiv,
tn.&f

1= 0

i~l

(23)

1 XZNSi,wa
n.<At

1 =O

iEIPER, skeSK

(24)

XOUTS;,,,,,

1= 0

igIPER, skESK

(25)

1= 0

IE L

(26)

rnEM

XOUTiv,

(v) molar balances for the mixers prior to each leading

_ XOuTSip,rk-

RM,,j.

XOUT,,,

XOiJTip.m

c
Id

(121

(14)

for the splitters in the outlet of

ksl

(viii) summation

mf e Mm-

XNSip,s*

1, rnEM

skfSK

-ZNi.XZNi.,=Om~M,

balances

1.m

. XINSip,sk+ 1.m = 0

ip E ZPFR,skESK,

Vi -

+ F%rq

_ XMRm,.m

- BPip.sr+ I . XINSip.sk+

7.2. Constraints of the synthesis problem

The desired objective is subject to a set of constraints constituted
by the mass balances and the
logical constraints. The mass balances include:

(13)

+ FRSip.ti,mf

(7)

where an upper bound is usually set for the total

operation time 0 of the plant.
The efficient utilization of the reactants can be
evaluated in terms of the overall yield defined as the
molar rate of desired products over the molar rate of
fresh feed reactants, the overall selectivity defined by
the molar rate of desired products over the molar
consumption rate of reactants and/or the overall conversion defined by the molar consumption rate of
reactants over the molar fresh feed rate of reactants.
Since detailed expressions are not generally possible
unless the particular reaction mechanism is available,
objective functions based upon these criteria are represented by the general symbol R.

. XINips,

mEM

mFMXFCr,,

Synthesis of isothermal reactor-separator-recycle

c Xi?,,,mEM
c XL,.,
ma&f

1 =o

1EL

(27)

l=O

ZEL

(28)

vi . Crp.m - Rr,,i = 0

INSi,.pk . XINSi,mt
-

ieIcsrn,

rl,

- OUTsi.

(29)

mEA

XOUTSi.,k_,

VSi,,~Cv,p.m.RS,p,i,,*
VP

= 0

iEIPFR,

k,, . f,,(CNi,,)

varconL < U
(30)

= 0

rp E RP,

i E ICSTR,
rnEMP

RS,p,i&

k,p S,p (CNSi.sk,m)

where the outlet concentrations

molar fractions as:
CNi,,

c XOUTi,m.
( me&f

(31)

= 0

rp E RP, i E IPPR, s~ESK,

MV,,,

(32)

rn~M~

XOUT,,,

= 0

(x) molar balances

superstructure

FC,
D, -

XDL,

FC,

each

B, -

D, = 0
= 0

- XFC,,,

U-ZiCO

iEZ

(42)

-FC,

IEL

(36)

rnEMP6

(37)

mEMy

(38)

= 0

components

constraints

= 0

nEN

(39)

for the desired products,

2 PR,

u-

U . ZS+

< 0

iEIPFR,

i E IPFR, sk E SK

ZSi,,k 9 0

r, < 0

sk ESK

leL.

(43)
(4)
(45)

The

mathematical
formulation
can, in general,
all the proposed bypasses of the superstructure. In the considered examples the existence of a
bypass around a SCSTR unit is associated with the
existence of the particular unit according to the following logical constraints:
Bpi,sl; -

(35)

Di.XQ,,

r..
as well as the specifications

(xii) logical

the

1ELd
I.1.

XFCL,

Vi -

U (1

- ZSi,J

mEMdp

(40)

< 0

iEIPFR,

skESK.

Another set of logical constraints describes logical

sequences of units in the superstructure. Thus, if unit k
cannot exist without unit m an expression of the form:
var: d 0

would force vat-p to take the value of zero unless m is

an active unit (i.e., var: has the value 1). For our
problem, the following constraints of this type were
necessary:

>

+ ,e$d FC, . XFC,,,

c
rsp

(41)

varp -

(xi) molar balances for the intermediate

-

iEZ

= 0

IcL,

c Bi. X6,,
I6LE

of

EEL

>

XFCI,,

(34)

>

c
XFC,.,
( meMy

U.Zi<O

vsi.slr -

(33)

skESK

separator

IEL,

X%n .

handle

mEM,

c
XFC,<,
c ?nEA4f

c
XFC,,,
( nlEA#:~

lNi

FCi

iEiPFR,

around

which, since the continuous

variable
is always
positive, can be true only if uarrn is zero.
For the present formulation
the following
set of
these constraints was introduced:

= 0

>

zero

rrar;O< 0

INSi,,r,

C X0UTSi.sk.m . MVm
( rnEM
!

- XOUTSi,sL.m

while if the unit does not exist, varp becomes

and the inequality yields:

are given in terms of

~EI, rn~M
CNSi.s*,m

where VULVA
denotes the continuous variable associated with unit k, vary denotes the integer variable
that describes the existence of this particular unit and
U is a large number. If the unit participates in the
superstructure, varp takes the value of 1 and the
above inequality yields:

mEM.

The reaction rates I&,,,, and RS,,,.,ti.i can be expressed as a general functlonf,,
of the outlet stream
concentrations times the reaction constant k as:
R,p_i -

u . varpt 6 0

var; -

0 U Ti . X0 U T,,,

1373

The logical constraints are used in order to force a

continuous variable of a nonactive unit of the superstructure to take the value of zero. They are of the
general form:

(ix) molar balances around each reactor unit

IN, . XINi,,,

systems

ZSi&
ZSi&

- Zi < 0

ZSi,,k_l

< 0

iEIPFR,

skESK

(46)

iEIPFR,

skeSK

(47)

c
Ylc
Y,<O
HEN.
(48)
lEIj=r*
/ELFYJLP,:
.
Finally, since the reactor network should be active
and one optimal separation sequence is expected to
exist:
Czi3

(49)

&K=

1.

(50)

is1

1374

ANTONIS

C.

KOKOSSIS

and

A final set of constraints imposes that all variables are

non-negative
(non-negativity
constraints) or binary
variables (integrality constraints) and is defined as
FD,,

FRi,,,

D,, XFC,.,,

v,, I%.&,

MRi,,,

-X-B,,,,

&,,ir
zi,

INi,

XD,.,,

R.%~,i,,~, CNi,,t,
r,,

ZSi,Sk E (0,

OUT,

XMR,,,,

THE

PROPOSED

SOLUTION

2 0

CJJSi,,r,, 3 0

(51)

11.

(521

The
complete
mathematical
formulation
MINLP
problem is given in Appendix A.
8.

3 0

of

the

ALGORITHM

The optimization problem that is formulated in the

previous section consists of two types of variables:
continuous and integer variables. The integer variables participate linearly in both the objective function and the constraints while the continuous variables participate linearly and nonlinearly. The nonlinearities include the polynomial
expressions obtained
from the simulation data, the expressions of the reaction rates and the bilinearities associated with the
mass balances. Such constraints define a nonconvex
feasible region and therefore there is no guarantee for
the global optimum.
The proposed solution algorithm for the MINLP
problem is based upon a decomposition
of the original problem and iteration according to the Generalized Benders decomposition
algorithm. The algorithm suggests the solution of a sequence of nonlinear programming
(NLP) primal problems and mixed
integer linear programming
(MILP)
master problems
that are based upon the dual representation
of the
primal problem. The solution of each NLP problem
provides an upper bound (lower bound) for a minimization (maximization)
direction while the solution of
each MILP
provides a lower (upper) bound. The
MILP
solution also provides the integer variables to
project on the next NLP problem and convergence of
the algorithm is achieved whenever the MILP
master
problem fails to provide a new feasible integer combination.
The NLP subproblems
of the solution algorithm
are large scale nonlinear programming
problems and
initialization is possible by solving a so-called pseudoproblem
primaI NLP subproblem. The pseudoprimal
is the projection
of the full primal problem in the
subspace of the continuous variables that are associated only with the active units at the current iteration.
Around a small region of the solution vector of this
subproblem
a relaxed problem is next solved that
relaxes the equality constraints H(X) of the primal in
the form - a d n(x) d 0: and minimizes the infeasibilities CL.The solution vector of the relaxed problem is
used to initialize the primal problem. In the case where

CHRWCODOULOS

A.

FLOUDAS

an infeasible primal problem is found, the Lagrangian

multipliers that are associated with the next MILP
master problem are obtained by the solution of the
relaxed problem.
The suggested solution procedure which is included
in OASIS (Floudas, 1990) was automated in the computer program
ORESS
(Optimization
of REactor
Separator recycle Systems) that uses the high level
modeling
language
GAMS
(General
Algebraic
Modeling
System) and the algorithmic development
methodology
APROS (Paules and Floudas, 1989). At
each iteration the program
calls the appropriate
solvers for the various subproblems, updates relevant
parameters and checks for stopping criteria. If the
criteria are met it stops, otherwise it continues to the
next iteration.
inDue to the nonconvex
type of nonlinearities
volved in the mathematical formulation, infeasibilities
are very likely to occur in the NLP subproblems in
the case where improper initialization has been used
or inappropriate
bounds have been allowed for the
continuous variables. In order to avoid unfortunate
solution trials, ORESS dynamically sets and updates
lower and upper bounds for all variables, generates a
number of different starting points at each iteration
and makes use of all of these points before it declares
as infeasible
a nonlinear
programming
(NLP)
problem.
The proposed approach is general and, under the
assumptions imposed in Section 2, accounts for all
possible structural and operational alternatives of the
reactor-separator-recycle
system. As an offset to the
advantages
of the approach, however, one should
consider that the solution algorithm is restricted to
provide a local solution. The solution, which evidently
depends on the initial starting point, cannot be
ciaimed to represent the global optimum, the search of
which is not addressed by this paper. The global
optimum
search for nonlinear programming
and
mixed integer programming problems is itself an area
of research and newly developed techniques that have
provided promising results might also be proved applicable for the reactor-separator-recycle
synthesis
problem as in the proposed formulation.
In the following section, the potential of the presented algorithm
is illustrated
in two different
examples of chemical processes by considering
a
variety of specifications for the reactor network and
the desired products, as well as by optimizing in terms
of different objective functions.
9.

EXAMPLES

9.1. Benzene chlorination

The design of a benzene chlorination
process is
considered as a first example. The chemical reactions
of this liquid-phase process are given as:
C,H,

+ Cl, -

C,H,Cl

+ Cl, -

kl
LZ

C,H,Cl
C,H,Cl,

+ HCl
+ HCl.

Synthesis

of isothermal

reactor-separator-recycle

Further chlorination reactions can also take place

but since they involve insignificant amounts of reactants they have been considered to be negligible.
The kinetics of the process were studied by McMullin
(1948), who showed that the chlorination of benzene
(A), monochlorobenzene (B) and dichlorobenzene (C)
is in all cases first-order and irreversible.
In the reaction level, pure A reacts to the desired
product B, waste product C and hydrochloric acid.
The kinetic constants are k, = 0.412 h- and k,
= 0.055 h - . The hydrochloric acid produced is
eliminated at the reaction level output by a stripping
operation whose cost is not taken into account.
Although all the reactions are exothermic internal coil
are used in the reactors to remove the evolved heat
and therefore keep the temperature in the reactors
constant.
In the separation level, unreacted A is separated
and recycled toward the reactor network, valuable
product B, of which the demand is assumed to be
50 kmol/h, and product C. The volatility ranking of
these components is aA > ug > cc,. Thus, the possible
separation tasks are: A/BC (column l), AB/C (column
2), B/C (column 3) and A/B (column 4).
Simulation results reported by Auzerais (198X) provided estimates for the capital and operating cost of
all the sharp distillation columns of the chlorination
process (purity specification: 99%) and are given
along with the cost expressions for the reactors in
Appendix B.
The synthesis problem was studied in four different
cases. In the first three cases, the objective was to
minimize the annualized total cost of a plant that
produces a minimum of 50 kmol/h chlorobenzene by
considering a variety of specifications for the reactor
network. In the fourth case, different objective functions were used and conclusions were drawn by comparing the different solutions. The postulated superstructure always consisted of four CSTRs and four
PFRs and each PFR unit has been approximated by a
cascade of seven CSTRs (SCs). The large-scale optimization problem included 947 continuous variables, 36

51.35

137.5

systems

integer variables and 1063 constraints. In all cases, a

MIPS RC 2030 workstation computer was used.
Case 1: utilization of a least number of CSTRs.
In
this case a minimum of two CSTRs is required for the
reactor network. The starting point of the algorithm
was one PFR and four CSTRs along with columns 2
and 4 and the optimal reactor-separator-recycle
system was found to consist of two CSTRs and 1 PFR
and columns 1 and 3. In the optima1 solution, shown
in Fig. 6, a fresh benzene stream (53.14 kmol/h) along
with a total recycle stream of purified benzene
(51.35 kmol/h) originating from the distillate of column 1, are feeding the first CSTR of the reactor
The
reactors
connected
in
a
network.
are
CSTR-PFR-CSTR
series combination and feature
volumes V,,,,
= 3.427 m3, V,,, = 10.565 m3 and
V ,-sTR = 3.482 m3 respectively. The production
of
chlorobenzene is the minimum required (50 kmol/h)
and the total annual cost is $314,361. The reported
solution was obtained in nine iterations with an average CPU time per iteration of 5.88 s per prima1 and
2.00 s per master problem.
and/or
PFRs.
No
Case 2: utilization of CSTRs
requirements were imposed for the reactor network in
this case. Providing an initial guess of one PFR and
columns 2 and 4, the minimum annual cost is found to
be 5304,911 and the optimal structure consists of a
single PFR and coIumns 1 and 3. Convergence of the
solution algorithm required five iterations with an
average consumption of 5.50 CPU seconds per primal
and 1.78 seconds per master problem. In the optimal
solution, shown in Fig. 7, both the volume requirements (V,,,
= 17.478 m3) and the total recycle from
the separation network (52.3 kmol/h) are greater than
in case 1. Fresh feed is required at a rate of
53.147 kmol/h and no splitting for any of the feeding
streams of the PFR was necessary.
Case 3: utilization of a least number of PFRs.
A
minimum number of three PFRs is required in this

kmolfir
50

II
A

d
B

kmoLbr

Fig. 6. Solution for the benzene chlorination process--case 1.

1376

ANTONIS

C. KOKOSSIS

and CHRISTODOULOS

A.FLOUDAS

52.31 kmobhr
t

Fig.

7.

Solution for the benzene chlorination processdase

case. The initial guess for the reactor-separatorrecycle system consists of four PFRs
along with
columns 2 and 4. The minimum annual cost is found
to be $309,840 and the optimal structure, shown in
Fig. 8, is an arrangement of three PFRs in series and
columns 1 and 3. The first PFR features a recycle
(10.10 kmol/h) and has volume Y PFR-L-- 5.562 m3
while the other two PFRs
have volumes
VPFR_a
= 5.734 m3 and V PFR-3 = 5.873 m3 respectively. Although a larger total cost is found for the plant, the
total volume requirements,
the fresh feed requirements (53.02 kmol/h) and the tota recycle from the
separation network (47.98 kmol/h) are less than in the
previous case. The solution algorithm converged in
two iterations consuming 6.24 CPU seconds per primal and 1.98 CPU seconds per master problem.
Case 4: multiple objectives. The importance of applying different performance criteria for the reactorseparator-recycle
system is next studied by solving
the synthesis problem using different objective functions. The different objectives include the profit of the
plant, the annualized cost of the plant and the overall
yield of the product. In order to facilitate comparisons
among the solutions obtained, a minimum production
of 50 kmol/h chlorobenzene is required for all but the
last of the presented examples.
(a) Profit: providing
CSTR
and one PFR

an initial structure of one

with columns 2 and 4, the

2.

maximum profit is found to be $1,224,038. The solution is obtained in two iterations and the average
CPU time is 5.56 seconds per primal and 1.85 seconds
per master problem. The optimal structure consists of
three CSTRs and columns 1 and 3 is shown in Fig. 9.
A fresh feed stream of 51.97 kmol/h is required and
the recycled benzene stream is 159.43 kmol/h. Both
the fresh feed and the recycle stream lead to the first
CSTR. The CSTRs are connected in series and are of
almost the same size: V,-STR_L= 4.88 m3, Vcsm_2
= 4.97 m3 and V,,,,_,
= 5.04 m3. The annual cost
of this plant is $321,158, the yield 0.314 and the
benzene conversion 0.326.
(b) Annualized cost: with the same initial structure
as in the previous example, the minimum cost is found
to be $293,324. The optimal structure, shown in Fig.
10, consists of two CSTRs with columns 1 and 3. The
CSTRs are connected in series and their volumes are
VCSI.R_I = 10.12 In3 and
V,,,,_, = 10.47 m3.
A
larger feed stream (54.45 kmoI/h) and a much smaller
recycle stream (54.23 kmol/h)
are required than in the
previous case. The profit associated with the plant is
$1,166,420, the yield 0.460 and the benzene conversion
0.501. The solution
algorithm
converged
in two
iterations consuming 5.275 s per primal and 1.86 s per
master problem.
(c) Overall yield (a): the maximum overall yield is
found to be 0.5653 and the optimal structure, shown
in Fig. I 1, consists of a single PFR and columns 1 and
3. The initial structure was one CSTR and columns 1

47 98 km&l-c

50 krnoLhr

10.10 kmol/hr

Fig. 8. Solution

for the benzene chlorination process--case

3.

Synthesis of isothermal reactor-separator-recycle

systems

L59.43 kmolfhr

1377
50kmol/hr

E
I3

Fig. 9. Solution for the benzene chlorination process-se

54.23 kmoyhr

-d

54.45kmolhm

4(a).

wm

V CSTB=10.12 In3

V csTR=10.47m3

Fig. 10. Solution for the benzene chlorination

process-ase

4(b).

50 kmolfhr

t
54.57kmoh

B
V

PFR

20.73~~~

Fig. 11. Solution for the benzene chlorination process+ase

and 3, and the solution algorithm converged in two

iterations with an average consumption of 5.48 CPU
seconds per primal and 1.85 seconds per master problem. In the final solution, the PFR has volume I,,,_,
= 20.73 m3 and does not feature any side streams.
The required fresh feed stream is 54.57 kmol/h and
much less recycle (33.87 kmol/h) is needed than in the
previous cases. The annual cost of the plant is
$785,509, the profit $667,109 and the benzene conversion 0.617.
(d) Overall yield (b): instead of a minimum production of chlorobenzene,
a minimum consumption
of 50 kmol/h of benzene is required. Starting from one
CSTR and columns 1 and 3, the optimal reactorCES 46-5/6-L

4(c).

separator-recycle
system consisted, as in the previous
case, of a single PFR unit with columns 1 and 3.
However, in the final solution, shown in Fig 12, a
PFR was at each upper bound (V,,,.,
= 30.0 m3), a
much larger feed stream is required (78.96 kmol/h)
and a larger recycle stream (49.00 kmol/h). Although a
larger annual cost ($840,214) and less profit (5615,405)
are found, the overall yield and the benzene conversion are, as in case (a), 0.5653 and 0.617 respectively.
The solution algorithm converged in two iterations
consuming 5.62 CPU seconds per primal and 1.75
seconds per master.
As might be expected,

the annualized

cost and the

ANTONISC. KOKOSSIS

1378

and

CHRISTODOULOS

A.

FLOUDAS

49.00 kmol/hr
t

78.96 kmob'hr

Fig. 12. Solution for the benzene chlorination process--case 4(d).

profit provide similar solutions that favour the CSTR

structure. The overall yield, however, results in a
different optimal structure, namely a PFR, an optimal
operation that accounts for 54.5% of the maximum
obtainable profit and an annual cost which is 267.8%
greater than the minimum possible. Furthermore, by
comparing the results from the last two examples, it
becomes clear that taking the yield as the performance
criterion of the reactor-separator-recycle
system, no
distinction can be made among solutions associated
with favourable annual costs and/or profits. Since a
synthesis problem based upon the maximization of
the overall yield does not actually take into account
the separation network but maximizes instead only
the performance of the reactor system, these results
should be considered indicative of the importance of
the coupling between the reactor and separator network and should lead to the conclusion that unless
the objective does not account for this coupling poor
design results are obtained.
9.2. Production
of ethylbenzene
In this example the alkylation
of benzene with
ethylene for the production of ethylbenzene is studied.
The process is an intermediate stage of the production
of styrene using the direct hydrogenation
method and is
carried out in the liquid phase. The following first
order reversible reactions describe this proces:
C,H,
C,H,CH,CH,

+CH,=CH,,
+ CH,

% C,H,CH,CH,
= CH 2 2 C,H,(CH,CH,),

Higher order alkylation products as well as other

high boiling
materials
that are obtained
as byproducts of the process were not considered here. In
the alkylators liquid benzene (A) reacts with a gaseous
stream of pure ethylene to produce the desired ethylbenzene (B) and the coproduct diethylbenzene (C). In
the separation level, B is obtained at a minimum rate
of 10 kmol/h while both A and C have potential
recycles to the reactor network.
The ranking volatility is aA > air > uc and, thus, the
possible separation tasks are: A/BC (column l), AB/C
(column 2) B/C (column 3) and A/B (column 4). For

each column separate simulations were necessary for

different feed flow rates and compositions. Details for
the simulations along with the expressions for the
venture costs of the distillation
columns and the
capital cost of the reactors are given in Appendix B.
In the following examples, a superstructure of
four CSTRs and four PFRs is postulated
for the
reactorseparator-recycle
system. With a required
minimum production of 10 kmol/h ethylbenzene, the
synthesis problem is solved by considering two different cases for the reaction kinetic constants of the
alkylation process. The objective is to minimize the
annual cost of the plant and the large scale optimization problem consists of 1050 continuous variables, 36
integer variables and 1133 constraints. An MIPS RC
2030 workstation was used for the computational part
of the solution algorithm.
Case 1. In this case the reaction constants used are:
k, = k; = k, = k; = 0.4 h-i.
Starting from a
structure of one CSTR and columns 2 and 4, the
solution algorithm converged
in six iterations and
consumed 6.12 CPU seconds per primal and 1.6 CPU
seconds per master problem. The minimum annual
cost of the plant is $79,272 and the optimal structure,
and
shown in Fig. 13, consists of a single PFR
columns 1 and 3. The required volume for the PFR is
V pFR = 3.68 m3 and the fresh feed benzene stream is
11.78 kmol/h. Although a total recycle of 36.28
kmol/h is found for the benzene, a relatively small
portion
(21.6%)
of the produced
diethylbenzene
(2.27 kmol/h) is recycled.
Case 2. In this case the reaction constants used are:
k, = k; = 0.4h-
and k, = k, = 4.0 h- . With
an initial structure of one PFR and columns 2 and 4,
the minimum annual cost is found to be $157,253. The
optimal structure, shown in Fig. 14, is a single PFR
and columns 1 and 3. The fresh benzene stream is
16.84 kmol/h and the volume of the PFR is V,,,
= 5.7X m3. In this case, a much larger benzene
recycle (223.57 kmol/h) is required and a larger
portion (40.5%)
of the produced diethylbenzene
(11.5 1 kmol/h) is led toward the reactor network than
in case 1. Such a result should be expected since the

1380
CNLc.,
costann
costpap
Cost-P
c*st+
D,
FL,,,
F&y,
FRSi,sk,,
FG
I
ICSTR

p-FR

IN,
INSi.sk

iced

Mbt
MY
MM,,,
MRSi,,.sk
MK,m
MV,

MXRC,,
MXSS,,
iv
N SK

ANTONIS

concentration

C. KOKOSSIS

of component

m~ M

and
of

OuTSi*sc
annualized cost of the plant
capital cost of column I E L
capital cost of reactor i E Z
operating cost of column 1E L
distillate product of column 1EL
total fresh feed stream of component

CHRJSTODOULOS

OUTi
O

outlet stream out of reactor iEZ

outlet stream out of subunit skE SK

uTsi.sk

reactor

PGrn
PRm
Profit
Rrp>i

mEM

fresh feed of reactant m E MI

component into reactor iE1
substream of FR+,, leading to subunit
sk E SK of reactor i E I PFR
total feed of column IE L
set of the reactors
set of the continuous
stirred tank reactors
set of the plug flow reactors
inlet stream of reactor i E Z
of reinlet stream into subunit skESK
actor i e IPFR
set of the leading columns
reaction
constant
for
reaction
path

REC,
RMi,,
RP
RR,,,

RRsi~,r

of

i E IPFR

total purge stream of component WIEM

minimum production of desired component m r Mdp
annualized profit of the plant
reaction rate of reaction rpE RF in reactor i4zl
total recycle of pure m E M
stream from reactor i E I towards leading
column I E J
set of the reaction paths
interconnecting stream from reactor i E 1
to reactor k E I
substream of RR,,* leading to subunit
skESK

vsi,sk

reaction rate of reaction path rp E RP in

subunit skE SK of reactor ieZPFR
set of subunits (SCs) that represent each
reactor i E ZPFR
splitters of each FD,,
splitters of each OUT,
sale price of component WEEM
large number
volume of reactor ieZ
volume of subunit sk ESK
of reactor

XFG,,

molar

X&t,,
XDm,,
XM%mr

FC,
molar fraction of component m EM in B,
molar fraction of component m E M in D1
molar fraction of component
me M in

RSrp,i,s:
SK
SL$
SLOU

rpERP

SP:,

set of the columns

set of 1EL columns with feed n E N intermediate
set of I EL columns with bottom n E N
intermediate
set of I EL columns with distillate no N
intermediate
set of EEL columns producing recycled
m E M}
component
set of Ic L columns producing recycled
M E Mdp) component
set of components
set of recycled components
set of fresh feed components
set of desired products
set of components participating in reaction path rp E RP
set of components feeding column I E L
set of components at the bottom of column IEL
set of components
at the distillate of
column IE L
reactor network recycle in front of column 1EL
substream of MRi,,
leading to subunit
sk E SK of reactor i E lPFR
recycle stream of component m E M to
reactor i
molar volume of rnE M
mixers prior to reactor i E FSTR
mixers prior to subunit sk E SK of reactor
i E IPFR
mixers associated
with each recycled
component rc E M
mixers prior to each leading column

sq <J
the set of intermediates
number of elements sk E SK

A. FLOUDAS

vi

iEIPFR

XZNm,i

xuu

Ti,sk,m

ML,,
molar
ZNi
molar

fraction

of component

rnE

in

fraction

of component

rnE M

in

fraction

of component

rnE

in

OUT,

XINSi,sk,nt

molar

fraction

of component

me M

in

XOUTS,,,

ZNSi,,,
molar fraction

of component

me M

in

Y,

OuTSi,sr,
binary variable

associated

with column

associated

with reactor

variable associated
of reactor i E IPFR

with subunit

1EL

binary
icl
binary

zi
ZSi.sk

sk E SK

variable

letters

II

payout time
income tax rate
fixed charge cost of reactor i E 2
variable charge cost of i E I reactor
total operation time of the plant
fixed charge cost of column 1EL
stoichiometric
coefficient of component
m E M in reaction path rp E RP
functional expression for the yield or selectivity

Synthesis of isothermal reactor-separator-recycle

REFF.RENCF.S

Aggarwal, A. and Floudas, C. A., 1990, Synthesis of general

distillation sequences for nonsharp separations. Currrput.
Chem. Engng (in press).
Aris, R., 1969, Discrete
Dynamic
Programming. Blaisdell,
New York.
Auzerais, F. M., 1988, Automatic synthesis of reactor/separator network configurations. Submitted as a second proposition at the Department of Chemical Engineering,
Princeton University.
Barona, N. and Prengle, H. W., March 1973, Reactor design
for liquid-phase processes. Hydrocarbon
Processes
63-79.
Benders, J. F., 1962, Partitioning procedures for solving
mixed-variable programming problems. Number. Math. 4,
238-252
B&hop, J. and Meerhaus, A., 1982, On the development of a
general algebraic modeling system in a strategic planning
environment. Math. Prog. Study 20, 1.
Bodman, S. W., 1968, The Industrial
Practice
of Chemical
Process
Engineering.
M.I.T. Press, Cambridge, MA.
Brooke, A., Kendrick, D. and Meerhaus, A., 1989, GAMS: A
Users Guide. Scientific Press, Redwood City, CA.
Chitra, S. P. and Govind, R., 1981, Yield optimization for
complex reactor systems. Chem. Engng Sci. 36, 1219-1225.
Conti, G. A. P. and Paterson, W. R., 1985, Chemical reactors
in process synthesis. Process Syst. Engng, Symp. Ser., No.
92, 391-397.
Floquet, P., Pibouleau, L. and Domenech, S., 1985a, Reactor
separator sequenws synthesis by a tree searching algorithm. Process Syst. Engng, Symp. Ser., No. 92, 415426.
Floquet, P., Pibouleau, L. and Domenech, S., 1985b, Pro&dures doptimisation de cascades de rOacteurs avec ou sans
recyclage. Chem. Engng J. 30, 1 l-2 1.
Floudas, C. A., 1990, OASIS: Discrete/Contintious
Optimization Approaches
in Process Systems.
Computer Aided Systems Laboratory, Department of Chemical Engineering,
Princeton University.
GeolTrion, A. M., 1972, Generalized Benders decomposition.
J. Opt. Theory Applic. 10, 234-260.
Guthrie, K. M., March 1969, Capital cost estimating. Chem.
Engng 114142.
Hartmann, K., 1979, Experience in the synthesis of optimal
chemical process systems. Proc. i2th Symp. on Computer
Applications
in
Chemical
Engineering,
Montreux,
Switzerland.
Hornibrook, J. N., 1962, Manufacture of styrene. Chem. Ind.
872477.
Kokossis, A. C. and Floudas, C. A., 1989, Optimal synthesis
of reactor networks. I. Chem. E. Symp. Ser., No.
114,
261-272.
Kokossis, A. C. and Floudas, C. A., 1990, Optimization of
complex
reactor networks-l.
Isothermal
operation.
Chem. Engng Sci. 45, 595-614.
Marsten, R., 1986, Users Manualfor
ZOOMIXMP.
Department
of
Management
and
Information
Systems,
University of Arizona.
McMullin, R. B., 1948, Chem. Eng. Prog. 44, 183-189.
Murtagh, B. A. and Saunders, M. A., 1986, MINOS5.0 Users
Guide-Appendix
A: MINOS5.1,
Technical Report SOL
83-20, System Optimization Laboratory, Department of
Operations Research, Stanford University.
Nagiev, M. F., 1964, The Theory of Recycle
Processes
in
Chemical
Engineering.
Macmillan, New York.
Nishida, N., Stephanopoulos, G. and Westerberg, A. W.,
1981, A review of process synthesis. A.I.Ch.E.
J. 27,
321-351.
Paules, G. E. and Floudas, C. A., 1989, APROS: algorithmic
development methodology for discrete-continuous
optimization problems.
Operations
Rss. J. 37, 902-915.
Pibouleau, L., Said, A. and Domenech, S., 1983, Synthesis of
optimal and near optimal distillation sequences. Chem.
Engng J. 27, 9-19.
Pibouleau, L., Floquet, P. and Domenech, S., 1988, Optimal
synthesis of reactor separator systems by nonlinear programming method. A.1.Ch.E.
J. 34, 163-166.

1381

systems

Rase, H. F., 1977, Chemical

Reactor
Design for Process
Plants, Vol. 2. John Wiley. New York.
Simulation Sciences Inc., 1985, PROCESS
Simulation
Program Input Manual.
Fullerton, CA.
Sittig, M., 1965, Chemicals from ethylene. Chemical
Process
Monograph
No. 8.

APPENDIX A. THE COMPLETE MINLP FORMULATION

Max Profit

or min Cost or max a.

Subject to:

+ a;+,XFC:.,

= 0
>

bf,

XFC&

>
CostfP

Cost=

Profit

1
a

cosp

i z

yizi

x
x
SP;t.FC,.;XFC,,,
IELdPrnEMdP
1.m
0. FD,

Cost-

FD,-_cFRi.,=O
iEl
XOUT,,,

c RR,,,
ILE,

+ FRi.,f
I

1
M&m,
?hrsh#-=

INi. XINi+,

id

mcMmf

XM&,,

= 0

u T,.m+

rt _Es)fRLr.slr.
- BP,,.,, + 1 . XIN%.,,
ip 6

= 0

mgM,

iEIs,

mffM

XIN.%p.sr,- I + OuTSip.slr- I XOUTSip,st- 1.m

+ 1 RRSi,ip.,k X0

vi

+ c Cost,P - p c cost;pe = 0
1.s
ZEl
1

- me-&SP,.

BPip.sk-

ai

fN%,sh+

XMR,..,
+

XJW,.,I,+

lpFR, skESK,

FRSi,wt.ml

1.m

,.,.a =

sk = 1, mrM

c FRzY~,,~.,,, = 0
r&SK

i E IPFR, m E Mm

RR,,+

x RRS,,,,,.,
Sk&K

= 0

iE I, ipEIPFR

MR,,,

= 0

iEIPFR,

FRi,,

.TkSK

MRSi,,..r

mcM

1382

ANTUNIS

c RR,,,
!sEI

. XOUT;,,

+ c RM,,,
1d
-

XINSip.,k

BPip,sk

~ OUT,;

and CHRISTODOULOS

XOUT;,,

OU TSic,sk

XUU

= 0

= 0

isl,

meM

TS,,s,k m

ipsIPPR,

skESK,

sk = N,,

-0

It tp

XOUTi,,

1
MM,,,
mIE.aP
-

XFC,,,,

IE.qI
REC,

REC,

XFC,,,

Vi ieJ,m~M

FC,-XFC,.,=O

. FG + lE~
z MM,.,

INS,.,k
w.,,

. XfG.,

FC,-

c MM,.,,
le.4

. XFC,,,

- CMR~*,,1e,

XMR,,,

+ PG,

.FC,

XFG.,

IN,~RM,.I.
i

A. FLOUDAS

. XOUT(.,

OUT{,

XOUTi,,,

C. KOKOSSIS

lJ.Zi<O

x
XFC,,;
f Er;;;

rnEM,

FC, = 0

ZSi&

mreM

PR,

mcMd*

2 0

iEI

U.Zi<O

iE1
ZSi,rt < 0

U - ZS,,,

i E IPFR, sk E SK

< 0

U.Y,<O

iEIPFR,

skeSK

IEL

ZSi.*I- ~ Zi < 0
= 0

nsN

is IPFR, skeSK

- ZS,.+,

i~i~~~, skESK

< 0

mr~ Mrc

xXMR,V.,
m

1 =0

mrEM

x XIN,,,
me%4

1 = 0

if i

p=

_M

XOUT,,,

XINSi,,r,,
nrEM
c

c XOUTSi,srs,
IncM

ieI

1 = 0

~ 1 = 0

ieiPFR,

~ 1 = 0

iEiPFR, skeSK

1 XFC,_,-nlEM
c X&.,
REM

FD,,
RMi,,

sk ESK

FRi,,,

MR,,,,

FRSi.,k,,>

OUTSi.st,

RR&A,*,

D,, XFC,,,,

X&n.,,

XINn..,,
vi,

XOUT,.,,,,,

VSi&

1sL

l=O

ICL

WM
IN,.

XINi,,

- OUT,.
-

Vi .I

INSi,ti

l=O

IEL

X~NS<.Ik,,

= 0

R rp,i RS.e.i.rk

k,, ~f,,(CNi.,l
-

1 XOUT,_,

= 0

! InEM

iEIcSTR,

XOUT,,,

ie IK,

c XOUTSi,,k,,
( s&f

= 0

M V,

XOUTSi,sL,m

XD,,,

x%n

XFC,.,,,

= 21 1,547.07.

Costypia

= 25,000.

nt~M,

1113.86.

Y2 -

= 0

XFC,.,)

XFC,.,=Q

(BU

+ 479.1 1. XFC,,,)

032)

Ya + FC,.

(6984.48

XFC,_,

Costypita = S&944.24.

3869.53

XFC:,,)

(B3)

Y4
1135.84.

(B4)

XFC+,FC,.

Operating
cost ofthe columns. For estimating the operating
cost of each column I, the heat duties in the condenser QC
and reboiler QR are necessary. Assuming that QF = Q, = Q,
the expressions are as follows:
Q1 = FC,

(3.003 + 36.106.

skESK

Q2 = FC,

(16.187

+ 16.831 .XFC,.,

Q3 = FC,

(26.212

+ 29.447.XFC,.,)

Q4 = FC,

(10.70 + 28.411

XFC,

.A + 7.706.

XFC,.,)(B5)

+ 42.141 .XFC,,,)
(B6)

IEL

= 0

> 0
z 0

FC,

= 0

1 XFC,.,,, -. XFC,,,
i m t Mf
>
c

CNS,.,,,,

IsL

1
XFC,<,
( mEMy

m EM,?-

meM

1
isIPFR,

FC,

skESK

FC,-El-D,=0
D, -

XFC,.,

CostC;

WIEM~

iEI,
CNS,.ssx,,

XOUTS,>;

Y, + FC,

+ 1135.84.

. M V,

2 0

EXPRESSIONS

(1010.40~ XFC,.,

i E lPFR, m E M

rpeRP,

) = 0

(369.05.

msM

- XOUTSi.,k.,

rp~R&,

= 0

k,, .S,dCNSi,s~.m

in IcsT,

OUTS,

D, 3 0

1).

Yi, ZS.,,,E{O,

Co~ty~~~ = 132,718.16-

~.p,m R,,.i

FC,,

L 0

XMR,.,,

CN,.,,

B: COST

3 0

INSi..r

Example 1
Capital COSLof the columns.

XOUT+,,

VSi,,r, .c Y,~.,, . RS,,,,,,

P

CN;,,

XD,,,

BPi.+
XD,.,,

RS,,,i..r,.

APPENDIX

OUT,

XINSi,,k.,,,,

R.,i,
Z;.

1 =0

INi,

MRS,.,n.+..

1f L, m E Mf
IEL, rnfMp

(87)

XFC,.,).

W)

Capital cost of reactors.

[II the first three cases examined
for the chlorination
process, the capital cost of the reactors is
assumed
to be independent
of its type and the following
expression has been used:
Cost;pa = 12,760.43

Zi + 14,059.78

. V,.

(39)

Synthesis

Table

1. Parameters

of isothermal

for example

Cost of utilities
Steam
Cold water

$21.67/10 kl yr
$4.65./10 kl yr

Sale and purchase prices

Chlorine
Benzene
Monochlorobenzcne

$19.88/kmol
$27.98/kmol
$92.67/kmol

Payout
Income

time
tax rate

reactor-separator-recycle

2.5 yr
0.52

Vencosr, = 41,357.320. Y, +

Costy$p

= 3894.938-Z,,,

Z,,,,

+ 8178.003. V,,,,
+ 49.332.715. VP,,.

(B11)

2
For columns 1 and 2 the simulations were performed at
50, 100, 200 and 300 kmol/h and covered molar compositions 40.0-53.5% of A, 3-Z%
of B and 4.5-24% of C. For
column 3 the flow rates were 20, 50, 70 and 90 kmol/h and

152.456. XFC,.,)

0312)

= 622,272.549, Yz - FC,

Vencosty

(562.283 + 633.467. XFC,.,

+ 389.655. XFC,,,)

@IO)

The cost of cold and hot utilities, the prices of the reactants
and products, and other parameters of the synthesis problem, are given in Table 1.
Example

FC,

(432.709 + 418.420. XFC,.,

-

= 25,794.255.

1383

the molar composition

of B ranged from 60 to 79.5%.
Finally, for column 4 the feed flow rates were 75, 85,90 and
95 kmol/h and the molar composition
of A ranged from 45
to 64.5%. The purity specification of the simulations was set
to 99%.
The annualized venture cost of each column was calculated from the simulation results and the values af the cost
coefficients
(payout time, income tax rate, unit price of
utilities) used in the previous example. Within relative error
less than lo%, regression analysis on the results provided the
following expressions:

In the fourth case, however, the capital costs of the reactors

(CSTRs
and PFRs) is type dependent and given by the
following expressions:
cos@$

systems

Vencost\ = 54,966.389. Y, +
(748.609. XFC,.,
Vencosty

= 40,526.895.

Yd +

@I31

FC,
-

588.673

XFC:,,)

(B14)

FC,

(382.765 + 432.315

XFC,,,).

0315)

The capital cost of the reactors was given by the expression:

Cust;Bpita= 12,760.43 - Zi + 14.059.78.
while the operating

Vi

cost was assumed to be negligible.

(B16)