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Integrating Product and Process Design With Optimal Control Acase Study of Solvent Recycling
Integrating Product and Process Design With Optimal Control Acase Study of Solvent Recycling
www.elsevier.com/locate/ces
Received 11 February 2005; received in revised form 21 August 2005; accepted 10 October 2005
Available online 6 December 2005
Abstract
This paper proposes the simultaneous integration of environmentally benign solvent selection (product design), solvent recycling (process
design) and optimal control for the separation of azeotropic systems using batch distillation. The previous work performed by Kim et al.
(2004. Entrainer selection and solvent recycling in complex batch distillation. Chemical Engineering Communications 191(12), 1606–1633)
combines the chemical synthesis and process synthesis under uncertainty. For batch distillation, optimal operation is also important due to the
unsteady state nature of the process and high operating costs. Optimal control allows us to optimize the column operating policy by selecting
a trajectory for the reflux ratio. However, there are time-dependent uncertainties in thermodynamic models of batch distillation due to the
assumption of constant relative volatility. In this paper, the uncertainties in relative volatility were modeled using Ito processes and the stochastic
optimal control problem was solved by combined maximum principle and non-linear programming (NLP) techniques. Then the previous work
of optimal solvent selection and recycling was coupled with optimal control. As a real world example for this integrated approach, a waste
stream containing acetonitrile–water was studied. The optimal design parameters obtained by Kim et al. (2004. Entrainer selection and solvent
recycling in complex batch distillation. Chemical Engineering Communications 191(12), 1606–1633), for this separation were used and the
optimal control policy is computed first without considering uncertainties by variable transformation technique. The deterministic optimal
control policy improves the product yield by 4.0% as compared to the base case, verified using a rigorous simulator for batch distillation. When
the stochastic optimal control policy was computed representing the relative volatility as an Ito process, a similar recovery rate was obtained
from simulations, but the batch time was reduced significantly, producing the most profitable operation.
䉷 2005 Elsevier Ltd. All rights reserved.
0009-2509/$ - see front matter 䉷 2005 Elsevier Ltd. All rights reserved.
doi:10.1016/j.ces.2005.10.033
2002 S. Ulas, U.M. Diwekar / Chemical Engineering Science 61 (2006) 2001 – 2009
2. Integrated framework for waste solvent reduction 2.2. Solvent recycling—process design
As mentioned above, the integrated framework consists of At this stage the EBS selection and IPS recycling models
three stages: are simultaneously integrated. Three competing batch column
configurations: the rectifier, the stripper, and the middle vessel
(1) Environmentally benign solvent selection (EBS). column are considered which are given in Fig. 2. Heuristics and
(2) In-process solvent recycling (IPS). optimization are used to find the best possible column configu-
(3) Optimal control and operation. ration. A multi-objective optimization framework with possible
objectives: maximum product recovery, maximum column fea-
2.1. Solvent selection—product design sibility and minimum heat duty provide the various trade-offs
necessary for a smooth and robust operation. Kim et al. (2004)
The first stage of this integrated framework is product design applied this framework to an industrial case study involving
which is an approach to generate candidate solvent molecules acetonitrile (ACN) and water and derived two innovative batch
that have desirable physical, chemical, and environmental prop- campaigns. In this paper, to further improve waste reduction,
erties. Computer-aided molecular design (CAMD) is one com- optimal operation is also considered as well as product and
monly used method. Based on the reverse use of group contri- process design, which is described in the following subsection.
bution methods, CAMD can automatically generate promising The same case study will be used to see the effect of optimal
solvent molecules from their fundamental building blocks or operation on process recovery in Section 4.
groups (Kim and Diwekar, 2002a). Solvent selection model in-
cludes properties such as (a) distribution coefficient, (b) solvent 2.3. Optimal control—optimal process operation
selectivity, (c) physical properties like boiling point, ash point,
density, and viscosity, (d) toxicology, (e) environmental prop- The final stage of this integrated framework is to apply op-
erties like LC 50 (lethal concentration at 50% mortality), LD 50 timal operation strategies to achieve maximum product yield
S. Ulas, U.M. Diwekar / Chemical Engineering Science 61 (2006) 2001 – 2009 2003
Product Purity
Reflux Ratio
Variable reflux
Optimal control
Time Time
3.2. Time-dependent uncertainties solvent selection and solvent recycling steps of this framework
were simultaneously integrated.
The thermodynamic uncertainties represented in Fig. 4 are The two campaigns can be summarized as follows:
static uncertainties, which in most cases can be represented by Campaign I : Water separation/purification. In this campaign,
probability distributions functions. However, since batch distil- pure water is separated from the ACN–water mixture for direct
lation is of unsteady state nature, static uncertainties are trans- disposal of water to sewers. The water is the lower volatile
lated into time-dependent (dynamic) uncertainties, which affect component and the composition of the mixture is such that the
the optimal operating conditions. ACN mole fraction is low (xACN = 0.2235, xwater = 0.7765).
Recently a paper by Rico-Ramirez et al. (2003) presented Campaign II : ACN separation. In this campaign ACN is sep-
a new approach to optimal control problems in batch distil- arated using an entrainer that is designed by CAMD approach
lation under uncertainty. In this paper, Real Options Theory as described in Section 2.1 and a batch extractive distillation
from finance literature was used to include time-dependent un- process is employed to separate ACN. The candidate solvents
certainties in current formulations of batch distillation optimal that were found by Kim et al. (2004) were acetone and propyl
control. It was proved to be very useful for an ideal system of amine.
pentane–hexane (Ulas et al., 2003) as well as non-ideal sys- This paper focuses on the first campaign where the pure wa-
tems (Ulas and Diwekar, 2004). These time-dependent uncer- ter is obtained from ACN–water mixture. Since water is the
tainties were included in the process models by using a class of lower volatile component (LVC), general heuristics presented
stochastic processes called Ito processes. The uncertainties in by Kim and Diwekar (2000) suggest that a middle vessel or a
group contribution methods (UNIFAC) used for the estimation stripper can be used for this operation. Considering the remain-
of phase equilibria and their effects on the model parameters ing performance indices suggests the use of a middle vessel
were also illustrated in the work by Ulas and Diwekar (2004) column. A middle vessel with an infinite reflux ratio and a fi-
using extensive experimental data available in literature. nite reboil ratio is designed to obtain the best performance. The
Two examples of Ito processes are given in Eqs. (1) and middle vessel column has five theoretical equilibrium stages
(2). The first equation represents geometric Brownian motion, at the top and bottom sections. At the end of batch stripping
which was used previously for ideal systems and the second operation, the optimal design has the following parameters:
equation is for geometric mean reverting process, for non-ideal Rb = 5.1, Vt = Vb = 77.8 kmol/h, t = 4.08 h. We have simulated
systems this operation with MultiBatchDS䉸 (Diwekar, 1996), using a
semi-rigorous simulator, with zero holdup and 83.05% recov-
dx = x dt + x dz, (1) ery was obtained from this operation. This is used as our base
dx = (x − x) dt + x dz. (2) case in this study.
√ This high recovery was obtained for a constant reboil ratio
In these equations dz = t dt, where t is a random num- of 5.1. In this paper we suggest the use of an optimal reboil
ber drawn from a unit normal distribution. It was shown that policy to increase the product recovery. Using this method we
the stochastic reflux ratio profile improves the process perfor- are coupling the optimal design parameters found by Kim and
mance significantly as compared to the reflux ratio profile com- Diwekar (2000) with the optimal control policy derived for the
puted by deterministic approaches. An improvement in product batch stripper. This integrated approach is expected to increase
yield of 69% was reported (Ulas and Diwekar, 2004) in a case the performance of the batch operation. First we need to show
study involving the non-idel mixture of ethanol–water. In the that the optimal reboil policy indeed results in the most prof-
case of ideal systems such as pentane–hexane, the product pu- itable operation by increasing the product yield. The following
rity was improved by 11% (Ulas et al., 2003). We are using section presents a derivation of the optimal reboil policy simi-
this approach to obtain optimal reboil policy for ACN–water lar to optimal reflux policy reported by Diwekar (1992) where
separation. In order to solve this problem, we derived the op- the shortcut method for the batch stripper is used to simplify
timal reboil policy deterministic profile first, followed by vari- the problem and to decrease the number of state variables and
able transformation to accommodate for azeotropes. Stochastic the optimal control problem is solved using the combined max-
optimal reboil policy is derived in the next section. imum principle and NLP approach.
4. Case study
4.2. Optimal reboil policy—deterministic case
4.1. Acetonitrile–water separation—campaign I & II
The formulation of the maximum bottom product problem
ACN is a commonly used solvent in pharmaceutical and for the deterministic case is given below based on Pontryagin’s
specialty chemical industries. For example, ACN is consumed maximum principle. The aim is to find the optimal trajectory
to purify peptide drugs in liquid chromatography columns of the reboil ratio to maximize the yield of the key component,
(Mallinckrodt Chemicals, St. Louis, MO), however, at the end (LVC), for a given purity. In the formulation given below, bot
of the process a mixture of water and ACN is produced as a is the bottom product, S is the amount remaining in still which
waste stream which forms an azeotrope. Kim et al. (2004) stud- is also the first state variable x1 , xs (k) is the still composition
ied the separation of this mixture in two campaigns where the of the key component which is the second state variable x2 ,
S. Ulas, U.M. Diwekar / Chemical Engineering Science 61 (2006) 2001 – 2009 2005
(k)
Table 1 dzt Vb jx Vb (k)
Short-cut method for the stripper (Lotter and Diwekar, 1997) = −zt 1 − bot − (zt )2 (x2 − xbot ). (10)
dt Rb x1 jx2 Rb x12
Differential material balance equation
(k) (i) (i) For stripper:
(i) (i) xs (xbot −xs )old
xsnew = xsold + (k) (k) .
(xbot −xs )old (k)
x1 − zt (x2 − xbot )
Rb = (k)
. (11)
Hengestebeck–Geddes equation zt (jxbot /jRb )
−CB (i)
(i) xs (k)
xbot = i (k) xbot , i = 1, 2, 3, . . . , n. This solution is obtained by minimizing the Hamiltonian
k xs
which does not incorporate the purity constraint. Hence the
Summation of fractions
use of final boundary condition (zT = 0) provides the limiting
n
(i) (k) 1
solution resulting in all the still charge instantaneously going
xbot = 1, xbot = n .
i=1 i=1 (i /k )
−CB (x (i) /x (k) )
s s
to the bottoms pot (Rb = −∞) with lowest overall purity. Since
the formulation of the purity constraint is imposed external to
Fenske equation
Nbmin ≈ CB the Hamiltonian, the final boundary condition (zT = 0) is no
longer valid.
Underwood equations
n (i)
i xs
n
(i)
i xbot 4.3. Application of deterministic optimal reboil policy to
− = 0,
i
−Rbmin u = i − .
ACN–water separation
i=1 i=1
Gilliand correlation
Rb −Rb
min g N −C
As mentioned earlier, the optimal design with a constant re-
X= Rb ln(LK /H K ), Y = Nb +1B , boil ratio of 5.1 results in 83.05% recovery for ACN–water sep-
b
Y = 0.2478 − 0.0965 ln(3.784X),
Rbmin u −Rbmin g
aration. In order to see the effects of optimal reboil policy on this
Gb c = Rb . process, the formulation for the stripper was slightly changed in
order to incorporate the fact that a middle vessel with an infinite
reflux ratio was used for this separation. At each time step the
xbot (k) is the bottoms composition of the key component, Vb distillate composition was found using Hengestebeck–Geddes
is the vapor boil-up rate and Rb is the reboil ratio. equation for the top portion of the column
T T CT (i)
dbot dS (i) i xs (k)
Maximize J = or Maximize J = , xD = x .
(k) D
(12)
Rb 0 dt Rb 0 dt k xs
Maximize − x1 (T ) (3) In this equation CT should be equal to NT (number of the-
Rb
oretical equilibrium stages for the top portion of the column),
subject to
since we are using infinite reflux ratio. Also the differential
dx1 dS −Vb
= = , x1 (0) = S0 = F , (4) material balance equation for the still composition is changed
dt dt Rb
(k) (k) (i) (i) (k) (i) (i)
dx2 dxs xs (xbot − xs )old xs (xD − xs )old
= xs(i)
new
= xs(i)
old
+ (k) (k)
+ (k) (k)
.
dt dt (xbot − xs )old (xD − xs )old
Vb (k) (k) (13)
= (x2 − xbot ) dt x2 (0) = xF , (5)
Rb x1
Finally, the Gilliand correlation (Gilliand, 1940) is also dif-
and the batch stripper column model (Table 1) . ferent for the middle vessel. The equations for X and Y for the
Hamiltonian: bottom portion of the column are given as follows:
(k)
Vb Vb (x2 − xbot ) Rb − Rbmin g
Ht = −z1 + z2 . (6) X= , Y = 0.6187 − 0.5655X. (14)
Rb Rb x1 Rb
The adjoint equations are The rest of the equations are the same with the stripper since
dz1 Vb the reflux ratio is infinite.
(k)
= z2 (x2 − xbot ), z1 (T ) = −1, (7) It is known that ACN–water mixture forms an azeotrope.
dt Rb x12 The vapor liquid equilibrium data for a pressure of 760 mmHg
(k)
(Gmehling and Onken, 1977) suggests that the azeotrope occurs
dz2 Vb jxbot
= −z2 1− , z2 (T ) = 0. (8) at a composition around in 70%. The vapor liquid equilibrium
dt Rb x1 jx2 data is shown in Fig. 5.
Combine z1 and z2 , zt = z2 /z1 , The shortcut method for the stripper is based on the as-
sumption of constant relative volatility throughout the column.
dzt 1 dz2 d(1/z1 ) 1 dz2 z2 dz1 In case of azeotropic systems, the relative volatility becomes
= + z2 = − 2 , (9)
dt z1 dt dt z1 dt z1 dt unity at the azeotropic point so this assumption is no longer
2006 S. Ulas, U.M. Diwekar / Chemical Engineering Science 61 (2006) 2001 – 2009
1 1
top curve top curve
0.9 0.9
0.8 0.8
0.7 0.7
0.6 0.6
y1
y2
0.5 0.5
0.4 0.4
0.3 0.3
0.2 0.2
0.1 bottom curve 0.1 bottom curve
0 0
0 0.1 0.2 0.3 0.4 0.5 0.6 0.7 0.8 0.9 1 0 0.1 0.2 0.3 0.4 0.5 0.6 0.7 0.8 0.9 1
(a) x1 (b) x2
20 20
18 path 1
16 path 2
15
relative volatility
relative volatility
plate 1 14 path 3
plate 2 12
path 4
10 plate 3 10
8 path 5
plate 4
plate 5 6 +66% conf
5 4 -66% conf
2
average
0 0
0 0.5 1 1.5 2 0.0 0.5 1.0 1.5 2.0
(a) time (h) (b) time (h)
Fig. 7. (a) Time-dependent changes in relative volatility with respect to time and plate taken from a semi-rigorous model. (b) Representation of relative
volatility as a geometric mean reverting process with 66% confidence intervals.
10 6. Conclusion
for the rectifier, the optimal reboil policy improves the product References
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This financial support from NSF Grant #CTS-0353088 is in batch distillation: a real options theory approach’, INFORMS/CUSTOM
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