Computers

&Chemical
Engineering
Computers and Chemical Engineering 24 (2000) 225-229
www.elsevier.com/locate/compchemeng

Convex attainable region projections for reactor network synthesis

William C. Rooney a,*, Brendon P. Hausberger b, Lorenz T. Biegler a, David Glasser b
aDepartment of Chemical Engineering Carnegie Mellon University, Pittsburgh, PA 15213, USA
b School of Process and Material Engineering, University of the Witwatersrand, Johannesburg, Gauteng 20.50, South Africa

Abstract

This paper develops a systematic procedure for constructing an attainable region (AR). The approach uses two dimensional
ARs constructed in orthogonal subspaces to construct higher dimensional ARs. Our technique relies on previous algorithms that
provide a practical assurance of the completeness of ARs in two dimensions, using only PFR and CSTR reactors and mixing.
Here we build on a modification of this property by constructing 2D projections and their intersections that provide upper and
lower bounds of the AR. These bounds are then improved by applying AR constructions sequentially to candidate regions in
orthogonal subspaces. The approach is demonstrated on a well-known AR problem in three dimensions. 0 2000 Elsevier Science
Ltd. All rights reserved.

Keywords: Reactor network synthesis; Attainable regions

1. Introduction equipment. The application of an objective function

can be used in conjunction with the AR boundary to
The essence of the reactor network synthesis problem identify optimal structures. The AR and its properties
for a given set of kinetics, process conditions and have been outlined in a number of articles over the past
constraints is to find the optimal reactor network (units decade (Glasser, Hildebrandt & Crowe, 1987; Hilde-
types and sizes, etc.) that optimizes an objective func- brandt 8z Glasser, 1990; Feinberg & Hildebrandt, 1997;
tion. Although not as well developed as other areas of Feinberg, 2000). AR principles work well for small
chemical process design, great progress has been made problems, but beyond three dimensions, the geometric
in the past two decades on developing techniques to interpretations become complex. Lakshmanan and
solve the reactor network synthesis problem. Biegler (1996) combined AR concepts with superstruc-
Several methods have been proposed to solve the ture optimization. In their MINLP model, only forward
reactor network synthesis problem. Superstructure opti- connectivity between the reactors was assumed, leading
mization is one technique to solve these problems. to a compact mathematical representation. In addition,
Here, a fixed network of reactors is postulated and an their method was a constructive approach and did not
optimal subnetwork is found that optimizes a specified require an initial superstructure.
objective function. Recent superstructure optimization This paper continues using a hybrid approach of AR
contributions include the work by Kokossis and Flou- analysis with mathematical programming concepts. A
das (1990, 1991), Schweiger and Floudas (1999). systematic procedure is outlined to find the AR in three
On the other hand, attainable region (AR) theory has dimensions (3D) using a series of two dimensional (2D)
examined the question of what exactly can be produced AR projections. 2D projections have the advantage that
from a steady state reaction system. AR theory looks at only plug flow reactors (PFRs) and continuously-stirred
the geometric interpretations of various fundamental tank reactors (CSTRs) reactors need to be considered.
processes in state space, regardless of specific equip- Here we build on this postulate by constructing 2D
ment functionality. Only after a candidate AR has been projections and intersections that provide upper and
found is its boundary interpreted in terms of actual lower bounds of the AR. These bounds are then im-
proved by applying AR constructions sequentially to
* Corresponding author. candidate regions in orthogonal subspaces. This ap-
E-mail address:wrooney@andrew.cmu.edu (W.C. Rooney). proach also provides a novel interpretation of differen-

0098-1354/00/F% - see front matter 0 2000 Elsevier Science Ltd. All rights reserved.
PII: SOO98-1354(00)00518-4
226 W.C. Rooney et al. /Computers
tial sidestream reactors DSRs (a PFR with additional
feed distributed along its length) and PFRs that are
projected down into the 2D subspaces. The approach is
tested on a common kinetic scheme, frequently used in
reactor network synthesis problems.
2. Motivating example
To motivate this work, we start by presenting a
candidate AR for the reversible Van de Vusse kinetics
(1).
kLfB2C
A,
kzl kv
D assume that information is needed on the 2D AR in BC
The 3D AR in Fig. 1 was constructed using the guideli-
nes in McGregor’s (1998) thesis until this region sa-
tisfied all the AR necessary conditions. The boundary
of this AR is composed of a CSTR operating point,
PFR trajectories, DSR trajectories, and mixing lines.
If a designer is only interested in how much of
canpours -A
Fig. 1. 3D AR for the reversible Van de Vusse kinetics in ABD space.
Fig. 2. 2D AR for the reversible Van de Vusse kinetics in AB space.
and Chemical Engineering 24 (2000) 225-229
component B can be produced from (l), only a 2D AR
analysis is needed. Fig. 2 shows the 2D AR in AB
space, which is a subspace of the full 3D AR in ABD
space. Note the boundary of this 2D AR is composed
of a CSTR with bypass, followed by a PFR
with bypass. In addition, this 2D projection is a func-
tion of only the state variables A and B since the rate
functions
1
- klfA + k,,B - k,A2
byA - B&r + k,)
(1)
are completely described by the state variables. Now
composition space. The rate vectors in this space are
Besides the variables of interest, these rate expressions
also involve component A. Here, the value for A is free
and can be chosen to extend the BC AR the furthest.
Thus, it functions as a control variable in BC space.
Moreover, the choice of A must be attainable. The
addition of the control variable A in the BC space
makes the construction of the 2D BC AR more difficult
than the AR in AB space.
3. A systematic method for AR construction
McGregor (1998) outlines an exhaustive, trial-and
error search procedure in state space for finding a
candidate AR. A boundary for the candidate AR is
postulated. The necessary conditions for the postulated
AR are then checked. If any necessary conditions are
violated, another candidate AR is postulated and the
procedure repeats itself until a region satisfies all the
necessary conditions. For 2D AR problems, previous
experience has shown that only CSTRs, PFRs, and
mixing lines are needed to find a candidate AR. In
addition, visualizing the AR in 2D is an easy exercise
and can be used to reliably solve the reactor network
synthesis problems for small problems. For higher di-
mensional problems with three or more independent
variables, DSRs may also exist in the AR boundary. In
addition, AR problems of larger dimension cannot be
easily visualized.
We propose a four step algorithm for finding a
candidate AR by constructing a series of 2D ARs in
state subspaces. These 2D subspaces can be con-
structed using special interpretations of PFRs and
CSTRs.
 W.C. Rooney et al. / Computers and Chemical Engineering 24 (2000) 225-229
Component B
Mixing Points k&h DSR Point
PFR Point m CSTR Point
..
Fig. 3. Initial AR in the O,,,, subspace.
3.1. Initialization
We start by constructing points in nD known to be
attainable. These points are obtained by solving the
PFR and CSTR design equations from the feed. The
existence of critical DSRs (Feinberg, 2000) can also be
checked along the initial PFR and CSTR data. These
trajectories and loci provide a couple of key pieces of
information. First, they provide initial guesses for the
nD AR. Additionally, these points provide feasible
compositions to use as control variables and possible
mixing points in the families of subspaces. These points
are stored in Sk~99’“,the initial set of attainable compo-
sitions (where k is an iteration counter).
3.2. Intersections in state subspaces
We transform the nD AR problem into a series of
2D problems by working in a series of 2D AR sub-
spaces. This is accomplished by working in each one of
the *2 possible combinations of state variables. We
0 composition.
define a candidate 2D AR in the subspace of larger
dimensional ARs (particularly 3D in this paper) as an
orthogonal subspace. In composition space, this re-
quires the remaining n - 2 compositions be (advanta-
geously) available for mixing to remain in the subspace
of interest. For example, one might work in the BD
subspace, OBDIA, which is orthogonal to component A
(component C is found by mass balance and stoi-
chiometry). In BD space, component A must be held
fixed to any desired value by mixing with another
attainable point outside of the subspace considered. To
create an entire family of 2D ARs in BD subspace
requires a variety of values for component A. Thus, A
is the control variable when looking at 2D ARs in the
221
0 BD.LA subspace. The number of ARs in each subspace
is determined from Eq. (2).
ACk = max<c9-min(d i= l,..., n
1 (2)
NP ’
In this work, we set NP = 10 points along each axis of
the AR. Also, the range of the parameters can change
as extensions and contractions (unattainable regions) of
the subspaces are found. Initial ranges for each axis of
the AR can be obtained from S’.
Initial points in each subspace are found where the
data in Sk intersects the subspaces. These intersection
points consist of the PFR and CSTR operating points
generated from the feed, and possibly DSR operating
points. Additional intersections in the subspaces may be
generated by mixing points along the trajectories and
loci stored Sk (mix from the end of a PFR trajectory
back to the feed, etc.). After these points are found in
the subspaces, they are convexified by simple mixing.
This forms the initial candidate AR in each of the
subspaces. Fig. 3 shows an example of this process.
3.3. Extending the 20 subspaces
This section outlines how the initial 2D ARs (sub-
spaces) found in Section 3.2 are extended using varia-
tions of traditional 2D AR analysis. The constraint of
working in subspaces, where some components are
fixed to certain values, requires modified interpretations
of PFRs and CSTRs.
The vector equation describing the change in compo-
sition for each component using reaction, ran@, and
mixing, 0 = (c* - c)E~?, is:
ac
& = r(c) + /9o(c*, c) (3)
Here, CE%I”is the vector of compositions, l3 is a non-
negative scalar that controls how much mixing takes
place relative to reaction, c* is an attainable mixing
point, and r is an independent variable of integration.
Eq. (3) is used to maintain a constant control
Two instances of CSTRs appear in the subspaces. If
points are found in the subspaces where ac/& = 0 (in
Eq. (3)) for all components c, a CSTR with residence
time /3 can be used to achieve that point. For example,
this point could be obtained by solving the CSTR
design equation from the feed and looking where its
locus intersects each subspace.
However, another instance of CSTR points in the
subspaces occurs as a result of projecting points from
nD into the 2D subspaces. Let ci c c and c, c c be the
control variables and the subspace variables, respec-
tively. At the fixed CSTR point c, in a subspace,
a~,/& = 0, otherwise the current point c, could move
outside of the subspace via some combination of reac-
228 W.C. Rooney et al. /Computers
tion and mixing. No such requirement is imposed on
the control variables cj since these components of the
reaction and mixing vectors are not restricted to lie in
the plane of the subspace. In addition, the current point
c, must result in feasible, non-negative values of p.
Feasibility can be checked from:
which follows from (3).
Points satisfying the above conditions are produced
from iso-compositional CSTRs (iCSTRs), which we
define as a 2D CSTR that operates at a point where
&Jar = 0 for only the variables in the subspace. iCSTR
points can be achieved from either a DSR (/I > 0) or
mixing to a PFR (p = 0) in higher dimensions.
The analysis of PFRs must also change in the 2D
subspaces. Like the CSTR, a PFR cannot be operated
in the traditional manner in the subspaces. To achieve
constant composition of the control variables, material
must be mixed in along the length of a PFR. Thus,
iso-compositional PFRS (iPFRs) are needed to do the
2D AR analysis in the subspaces, not actual PFRs. The
mixing policy in these iPFRs, /?, is chosen to maintain
the control variables at their fixed value in the sub-
space. Eq. (3) shows the iPFR design equation. It
differs from the PFR design equation by the addition of
the mixing term, /?(c* - c). It should be noted that p is
not the mixing policy calculated by Feinberg (2000)
that ensures a DSR rides along the boundary of the
AR. Thus, iPFRS in the subspaces act in a similar
fashion to the isothermal DSR found by Nicol, Hilde-
brandt and Glasser (1997) where the control policy is
chosen to maintain constant temperature, whereas here
we will be fixing one or more composition values.
Mixing is also considered in the 2D subspaces. The
process of mixing ensures that each subspace will be
convex as any nonconvexities in the region can be filled
in by mixing. Mixing in the subspaces follows the
normal lever rule (4). Composition c in the subspace
can be achieved by the linear combination of any two
attainable points in the same subspace, c1 and c2,
weighted by the positive scalar 1.
c = /Ic, + (1 - A)c,
01111
Now, the initial candidate ARs in the subspaces can be
extended using the properties outlined in the preceding
paragraphs. Points from the ARs are sought where the
fundamental processes of reaction and mixing using
iCSTRs and iPFRs point out from the current AR in
the subspace. These extensions can always be made
convex since mixing is considered in all of the
subspaces.
and Chemical Engineering 24 (2000) 225-229
3.4. Additional intersections and extensions in 20
subspaces
The data generated from the extensions of all the
subspaces is recombined into the nD set Sk. Now, we
consider new intersection points in the subspaces that
are generated from the data in Sk. For instance, the
family of subspaces OBDIA contains information about
all components in the system. Points obtained from this
subspace can be projected into the other orthogonal
subspaces. These new intersections will either lie within
the current candidate subspace or they will lie outside
of it. If the former occurs, no extensions can be consid-
ered from that intersection since that point is already
attainable (i.e. any interior point can be obtained by the
appropriate mixing of boundary attainable points).
However, intersection points lying outside of the cur-
rent candidate AR may be candidates for extending the
subspares by simple mixing and possibly by additional
reaction. The process repeats until no further intersec-
tions can be created in any of the subspaces from the
set Sk.
4. Algorithm to construct nD ARs using 2D subspaces
Here, we summarize the algorithm outlined above.
1. Initialization
1.1. Initialize counter, k = 0
1.2. Initialize set So with:
_ PFR trajectories from feed.
- CSTR loci from the feed.
_ Critical DSR trajectories (Feinberg, 2000) (if
they exist).
- Mixing vectors along each trajectory and loci.
2. Subspace initialization
2.1. Determine initial range of each variable Ack
using Eq. (2)
2.2. Initialize subspaces, 0,” j = 1,. . . , NP using inter-
sections between the data in Sk at the values of
Ack
2.3. Convexify points in 0: j = l,..., NP forming
initial candidate ARs in the subspaces
3. Subspace extension
3.1. Extend subspaces O;j= l,..., NP using:
_ iPFRs
_ iCSTRs
(4)
3.2. Convexify extensions in subspaces using mixing
4. Subsnace recombination
4.1. *Increment iteration counter k = k + 1
4.2. Add subspace extensions to Sk
4.3. Project points from Sk into the subspaces
4.4. If any points from Sk provide feasible extensions
to the subspaces, GOT0 (2)
4.5. If no points from Sk extend the subspaces,
STOP.
 W.C. Rooney et al. /Computers
0 0
CarpDnentB cMlpMlew*
Fig. 4. AR in ABD space found using proposed
5. Results
In this section, we apply our new proposed algorithm
to the 3D AR reversible Van de Vusse kinetics (1) in
ABD composition space.
The algorithm developed above was implemented in
MATLAB. The proposed method found the 3D AR in
Fig. 4 in three iterations. The candidate AR closely
matches the AR found via traditional AR analysis in
Fig. 1. Here, the algorithm correctly finds the charac-
teristic features of the AR in Fig. 1. For instance, both
Figs. 1 and 4 show the maximum conversion to B in the
AR is 0.0702. The maximum selectivity of B/A is also
the same, 0.0873. Also seen in Fig. 4 are some of the
2D subspaces in BD space, constructed perpendicular
to the A axis, that where used in constructing the AR.
Total solution time to find the 3D AR was approxi-
mately 4 min on a Pentium II PC. This result is much
faster than the tedious construction techniques outlined
in McGregor’s (1998) thesis take to find a candidate
AR.
6. Conclusions
A systematic method has been presented to construct
candidate ARs. The technique uses convex combina-
tions of 2D ARs to construct larger dimensional ARs.
First, an initial nD AR is found by constructing points
known to be attainable. Next, a series of 2D ARs are
constructed in subspaces of the nD AR using modified
PFRs, CSTRs, and mixing points. These 2D ARs have
the advantage that they are easy to construct and
interpret. These 2D ARs are recombined to form an
and Chemical Engineering 24 (2000) 225-229 229
updated nD AR. Additional points of intersection may
be created, and the 2D ARs can be constructed again to
see if the nDAR can be extended. The algorithm was
demonstrated on a well-known reactor network synthe-
sis problem.
Future work will address several open issues in AR
research. First, only necessary conditions have been
derived in AR theory, not sufficient conditions. This
leaves open the question of whether a candidate AR is
the ‘true’ AR. Although experience has shown that 2D
AR problems can be solved reliably by CSTR, PFRs
and mixing lines, no formal proof of this exists. Thus,
the proposed algorithm may not be complete enough to
method.
find ARs. Additionally, the algorithm in this paper has
no guarantee of convergence, although other AR and
reactor network synthesis methods suffer the same fate
(Lakshmanan & Biegler, 1996; McGregor, 1998). It is
hoped that future work in finding AR sufficiency condi-
tions will shed light on developing complete AR and
reactor network synthesis algorithms.
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