Nicol 2001
Nicol 2001
Nicol 2001
Abstract
The attainable region (AR) technique is used to "nd the optimum process designs for an exothermic reversible reaction system
where allowance is made for cooling and heating with a constant temperature utility. The optimum process layout (equipment), which
results directly from solving the problem using the AR method, incorporates both a direct and indirect method of cooling material
undergoing reaction. The results have shown that direct cooling (cold shot) is favoured at high temperature and indirect cooling (heat
exchange) at lower temperature. The values of system parameters were changed and this caused the relative shape and size of the
attainable regions to vary. The inclusion of the cost of heating introduces a new complexity in the process layouts of the AR. In
particular the direct cooling (cold shot) is split into two stages: The hot reaction mixture is "rst cooled by adding preheated feed of
varying temperature and this is followed by the addition of cold feed to the reaction mixture. 2001 Elsevier Science Ltd. All rights
reserved.
Keywords: Attainable region; Reaction systems; Optimization; Process synthesis; Process design
1. Introduction
The attainable region (AR) technique is used in this
paper to "nd the optimum process layouts for an
exothermic reversible reaction system where allowance is
made for cooling and heating with a constant temperature utilities, which we will refer to as external cooling
and heating. Systems with exothermic reversible reactions have always presented a reactor design challenge
because the optimum reactor requires both high temperatures at low conversions to favour high initial reaction
rates and low temperatures at high conversions to
achieve high equilibrium conversions. The previous emphasis of research has been to "nd optimum ways of
achieving the required falling temperature progression.
The optimum temperature pro"les for a range of di!erent
0009-2509/01/$ - see front matter 2001 Elsevier Science Ltd. All rights reserved.
PII: S 0 0 0 9 - 2 5 0 9 ( 0 0 ) 0 0 1 9 6 - 2
174
Hence by "nding the AR, the optimum process speci"cations to achieve points in the AR can also be found.
175
(1a)
*c
*c
(1b)
176
4. The system
Omoleye, Adesina and Udegbunam (1989) have shown
that a wide range of industrial exothermic reactions such
as polymerisation, isomerisation, oxidation and esteri"cation reactions have characteristics that are similar to
those having "rst-order reversible kinetics. A "rst-order
exothermic reversible reaction is thus considered, where
the reactant A reacts reversibly to form B (A & B). The
rate of formation of B is de"ned by
!E
) (1!x)
!A exp
!E
) (x),
(2)
(3)
177
given by
d h k
" A ( ! )"K ( !).
(5)
A
A A
dq
C
N
Note that the variable q is now a relative cost variable.
We thus have three variables, conversion, temperature
and relative cost, that we will use to describe the system.
Thus the characteristic vector c is de"ned as c"[x, , q].
The AR is de"ned as the set of all the possible c that can
be achieved by a steady-state system that uses only the
processes of reaction, mixing, cooling and heating.
The fundamental processes have to be de"ned as vectors in the c space. These vectors represent the instantaneous change of state variables c at a de"ned point in
space when each of these processes occur on their own.
Glasser et al. have shown that for the processes of reaction and mixing in this space, the vectors are given by
(6)
(7)
r (x, )
x !x
V
r(c)" ) r (x, ) , v(c, c )" ! ,
V
1
q !q
k(c)" K ( !) , h(c)" K ( !) .
A A
F F
1
1
(8b)
*r (x, )
V
) ( !). (9a)
A
*
dc
"r(c)#bk(c) (b'0),
dt
(9b)
178
The two conditions u(r,v) and u(r,k) can be geometrically interpreted as surfaces. The surfaces are conditions only in terms of conversion and temperature and
can therefore be plotted in the x space as pro"les seen
in Fig. 1. It is interesting to note that u(r,k) lies slightly
above W . If cooling could have been done without any
cost (K "J) Eq. (8) would have reduced to
A
*r (x, )
V
"0,
(10)
*
which is the condition for the optimum temperature
pro"le and hence u(r, k) would correspond to W . The
optimum temperature pro"le can therefore be seen as
a possible generating intersector for reaction and cooling
where only reaction residence time adds to the cost (i.e.
cooling has no cost). The optimum combination that will
extend the AR the furthest for a process where the cost of
cooling adds to the total cost u(r, k) will di!er from the
W as can be seen in Fig. 1. It should be noted that the
optimum temperature proxle can still in principle be obtained with this system, it will however not lie on the
boundary of the AR but in the interior.
7. Example 1
7.1. Specixcations and conversion-temperature limits
We start with an example where only the processes of
reaction, mixing, preheating and cooling are considered.
To simplify the problem the cost of preheating is assumed
to be negligible. Before the construction of the AR can
begin one needs to de"ne the ranges of conversion and
temperature that we wish to consider. From Fig. 1 one
can see that the conversion is restricted by the equilibrium
line (W ). The equilibrium line is therefore one of the
boundaries in the x space. We furthermore restrict our
system by allowing preheating only to a temperature of
450 K. From this maximum allowable preheating temperature the temperature can still increase as a result of
adiabatic reaction. We therefore de"ne the adiabat with
"450 K up to equilibrium (AB) as another edge of the
AR in the x space. As no heating process is allowed
(except for the preheating), we can see that this adiabatic
edge cannot be crossed. Furthermore we de"ne the adiabat
with "300 up to equilibrium (CD) as another edge. The
conversion, temperature edges can be seen in Fig. 2. Note
that all x points inside the region ABCD are in principle achievable but we need to "nd out at what cost. For
the "rst example we choose the value of K as 150.
A
7.2. Constructing the AR!
Once the edges of the AR! are de"ned, the construction process can begin. The AR! is de"ned by its
Table 1
Optimum adiabtic reactor sequence
179
180
extended cooling surfaces ((k\, v>)!). Switching intersector 8 is the switch over between cooling surface E to
mixing surface H and switching intersector 9 is the
switch over between cooling surface G to mixing
surface I.
All the surfaces have to be tested to show they satisfy
the AR necessary conditions. If all the necessary conditions are satis"ed, which was the case for the example
under consideration we can say that the region obtained
is a candidate for an attainable region. The candidate
boundary can now be used to determine the optimum
process layout for the system.
7.3. Process layouts on *AR!
181
Table 2
Process layouts of *AR! for Example 1
On the reaction surface C there is a switching intersector 7 where we switch over to the cooling surface E and
from this surface there is a switching intersector 8 where
we switch over to mixing with the feed H. In Table 2 it
can be seen that the layouts of these regions branch o!
the main pathway layout (as do all the layouts). The PFR
is the process unit on the boundary that takes one
to the DCR . Once the operation
from the DSR
starts on the DCR
the corresponding reaction F and
cooling surface G de"ne *AR! and the process layouts of
these sections can be seen as primary branches of the
main pathway layout. On the cooling surface G there is
a switching intersector 9 where we switch over to mixing
with the feed. Intersector 9 joins smoothly with intersector 8 as surfaces E and G join smoothly.
182
9. Example 2
The K value for this example is chosen as 400. This
A
implies that the cooling costs are a lot cheaper than that
of the previous example. The x-projection of *AR! of
this example can be seen in Fig. 5. It will be noted that the
edges di!er from the previous example in that the righthand edge is an isothermal line at 550 K which represents
the maximum reactor operating temperature. The process layouts for the di!erent process surfaces can be seen
in Table 3. The three-dimensional presentation of *AR!
can be seen in Fig. 6.
One notes that the main di!erence between this
example and the previous one is the path that one uses to
the initial points on the generating intersectors. In this
example we need to distinguish between two kinds of
situations in which simultaneous processes occur. The
"rst one is isothermal while the second corresponds to
the generating intersector. The control variable for the
isothermal simultaneous operation is determined by
balancing the two processes such that the temperature
remains constant. The two types of isothermal simultaneous operation are the iso-DSR and the iso-DCR. For
the iso-DSR the di!erential sidestream amounts are controlled so that the temperature increase of reaction is
cancelled by the addition of cold feed. The iso-DCR
works on the same principle so that the reaction heat is
cancelled with utility heat exchange.
The iso-DSR on the maximum temperature line was
found to lie on *AR! along
. Once (r>, v>)! was
reached the main pathway on *AR! was the same as that
of the previous example (Fig. 4). The only di!erence was
that the switching intersector 7 between surfaces C and
D (also switching intersector 7 in the previous example)
was closer to the right-hand edge. Therefore (r>, v>)!
was shorter and this implies a smaller DSR on the
boundary pathway. It thus becomes clear that cooling
the reaction mixture by means of cold shot makes up
a smaller fraction of the total process layout. A smaller
DSR is used when cooling is cheaper and therefore
switching intersector 7 will gradually move to the right
as K increases. The process layouts of these
A
examples can be seen in Table 3. The main di!erences
between the "rst and the second example are the occurrence of the iso-DSR and the sizes of the optimum DSR
and DCR.
10. Example 3
For the third example the same AR edges were kept as
in example 2, but the K value was chosen as 2000 which
A
implies very cheap cooling relative to reactor volume
costs. The x-projection of *AR can be seen in Fig. 7. In
this example no (r>, v>)! was on *AR! as switching
intersector 7 of the previous example has moved out of
the de"ned edges. We do still "nd that the iso-DSR at the
maximum temperature provides the best initial isother). A point P is reached
mal reactor operation (line
where the iso-DCR moves into *AR!. For bigger
K values point P will move downwards on the isotherm
A
and for an in"nite K point P will be on the unreacted
A
feed baseline (x"0). From point P the iso-DCR (line
) is operated up to the u(r, k) pro"le from where
(r>, k>)! (optimum DCR) generates the cooling surface
D and the reaction surface E. Switching intersector 5 is
the switch over from the cooling surface B of the isoDCR to the mixing fan hull C. The optimum process
layouts can be seen in Table 4. These layouts di!ered
signi"cantly from the previous examples and showed
how varying the relative cost of reactor volume and heat
exchange area can change the layouts of *AR!.
183
Table 3
Process layouts of *AR! for Example 2
184
*x
K
*x
*
K
dv "
H
*x
*q
K
*x
*x
K
*
*
K
*
*q
K
*
*x
K
*q
1 0 0
*
K ! 0 1 0 .
*q
0 0 1
*q
K
*q
(14a)
x (t)!x(t)
K
v (c(t),c (t))" (t)!(t) .
K
H
K
q (t)!q(t)
K
(11)
The "rst condition for the (r>, v>). is that all points
H
along the generating intersector lie on the surface de"ned
by
(v (c, c );r(c))[dr(v (c, c ))!dv (r(c))]"0.
H
K
H
K
H
(12)
*c
*c *q *s (*c /*q ) *q
K,
K" K K " K K
(14b)
*c
*q *s *c
(*c/*s) *s
K
(*c /*q ) and (*c/*s) are the tangents to the preheating
K K
trajectory and (r>, v>)., respectively. These vector exH
pressions can be written for each of the single-vector
elements. By dividing the two resulting tangents we can
show that Eq. (14b) for one of its elements becomes
(*c /*q )x *q
P *q
*x
K" K K
K" V K,
(14c)
*x
(*c/*s)x *s
D *s
V
P and D are the tangents to the preheating and
V
V
(r>, v>). trajectories in the x direction, respectively.
H
Similar expressions can be obtained for the and q directional tangents. dv now simpli"es to
H
P
P
P
V
V
V
D
D
D
V
2
O
*q P
P
P
2
2 !I,
dv " K 2
(14d)
H
*s D
D
D
V
2
O
P
P
P
O
O
O
D
D
D
V
2
O
185
Table 4
Process layouts of *AR! for Example 3
(14g)
(v ;r)(dr(v ))!(v ;r)(dv (r))"0.
H
H
H
H
The second term of this equation falls away if Eq. (14f ) is
substituted in the above equation
(v ;r)(dv (r))
H
H
*q r
)r
1
" K V # V#
v (v ;r)h
H
*s D
D
D
V
O
O
!(v ;r)r"0.
H
(14h)
(15)
(16)
1
!
.
q "
) ln F
K K
!
N
F
K
(18)
Solving Eqs. (16)}(18) simultaneously allows us to determine the position of (r>, v>). in the three-dimensional
H
space. Eq. (12) can be used to determine as a function
K
186
(19)
(20)
X(c)v (c)
H
(21)
(r>, v>) ..
H
Projecting the (r>, v>). trajectory (RQ) in the xH
plane one sees u (v , k) in Fig. 8. One notices that it
H H
crosses u (v, k) (u (v, k) is the condition for reaction and
mixing to the feed point A). The crossing point of
u (v , k) and u (v, k) is the point where the correspondH H
ing mixing temperature on the preheating trajectory is
300 K, the feed point. From that point one can no longer
operate (r>, v>). as no colder temperature than that of
H
the feed is available. Such a point represents the end of
(r>, v>) . and will always lie on the cold feed u (v, k)
H
pro"le.
The maximum adiabatic rate line (W ) and the equi
librium edge (W ) are also given in Fig. 8. Di!erent
K values resulted in di!erent u (v , k) projections. The
N
H H
tendency was that smaller K values, implying higher
N
heating costs, resulted in u (v , k) projections that lay
H H
closer to the W
line. One notices that (r>, v>). starts
H
on W
(point Q) and that the u (v , k) pro"le intersects
H H
W
on the cold feed adiabatic edge. This intersection
187
188
189
Table 6
Process layouts of *AR! for Example 5
14. Conclusion
The AR technique has been successfully applied to an
exothermic reversible reaction system where allowance
has been made for both external cooling and external
heating with a utility of constant temperature. Using the
AR theory *AR! has been constructed for various systems. The e!ect of di!erent constraints on the process
and the e!ect of varying the cost parameters on *AR! has
been investigated and consequently the optimum process
layout changed.
190
Notation
x
c
r
V
*H
C
N
varied mixing
191
Mathematical notation
*p/*c
ab
a;b
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