# Computers and Chemical Engineering 24 (2000) 23 – 37 www.elsevier.

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**A method for simulation and optimization of multiphase distillation
**

V. Shyamsundar, G.P. Rangaiah *

Department of Chemical and En6ironmental Engineering, The National Uni6ersity of Singapore, 119260 Singapore Received 10 November 1998; received in revised form 10 January 2000; accepted 10 January 2000

Abstract Simulation and optimization of multiphase distillation are often required in the design and operation of process plants. In this work, a simultaneous solution method (~-method) is proposed and studied for simulating/optimizing two- and three-phase distillation. This method involves modiﬁcation of mole fraction summations such that the same set of governing equations is valid for different phase regions, and hence phase identiﬁcation and solution of the governing equations can be performed simultaneously and effectively. The optimization problem involved in the ~-method has a linear objective function and nonlinear constraints, and it can be solved using an iterated linear programming (ILP) or nonlinear programming (NLP) approach. The ~-method is applied to steady state simulation and optimization of two- and three-phase distillation. The results obtained for several examples and conditions are shown to be consistent and comparable to those in the literature. The t-method is successful for simultaneous simulation and optimization of multiphase distillation. For the distillation examples tried by the ~-method with the ILP approach, initialization based on feed is often satisfactory, major iterations (similar to those in Newton method) for convergence is 5 to 10, and CPU time on a personal computer is less than 1 minute. On the other hand, the ~-method with the NLP approach generally requires better initialization and/or more computations for convergence. © 2000 Elsevier Science Ltd. All rights reserved.

Keywords: Two- and three-phase distillation; Steady state simulation; Simultaneous solution method; Optimization

1. Introduction Distillation is the most important and common separation process in the chemical process industry. Although two phases, vapor and liquid usually exist in a two-phase distillation column, this phase pattern may change during the iterative calculations and/or for some limiting cases such as minimum reﬂux and minimum heat duty of the reboiler (Bullard & Biegler, 1993). In a three-phase distillation column, a second liquid phase may form on some or all stages in addition to the usual vapor and liquid phases in two-phase distillation. The main difﬁculty in simulating three-phase distillation is that the number of phases at equilibrium on a stage is not known in advance. If the assumed number of phases at equilibrium is more (or less) than that actually present, non-smooth problems (or pseudo solu* Corresponding author. Tel.: +65-8742187; fax: +65-7791936. E-mail address: chegpr@nus.edu.sg (G.P. Rangaiah)

tions) may be encountered during the simulation (Buzzi Ferraris & Morbidelli, 1982; Bullard & Biegler, 1993). It is difﬁcult to obtain the correct solution in both the situations. Existing methods for simulating three-phase distillation can be classiﬁed into two broad groups: equation decoupling methods and simultaneous solution (or global) methods. In the former methods, governing equations are partitioned into subsets (e.g. according to stage) and each subset is solved independently. Simultaneous solution methods consist of two steps: one, simultaneous solution of the governing equations for all stages based on assumed phases in each stage, and two, checking the results for stability of liquid phase in each stage to verify the assumption on the number of phases. Efﬁcacy of these methods for modeling three-phase distillation largely depends on the correct assumption on the phase pattern in the column. Cairns and Furzer (1990a), Gupta (1990) and Georgoulaki and Korchinsky (1997) proposed simultaneous solution methods for three-phase distillation cal-

0098-1354/00/$ - see front matter © 2000 Elsevier Science Ltd. All rights reserved. PII: S 0 0 9 8 - 1 3 5 4 ( 0 0 ) 0 0 2 9 9 - 4

and suggested precautionary measures. Georgoulaki and Korchinsky (1997) proposed the Napthali – Sandholm algorithm in its full version including energy balances and Murphree stage efﬁciencies for simulating three-phase distillation. A two-tiered approach was used for solving the model equations. ﬂow rate and composition of the feed to stage n. and the results will be discussed. a pseudo temperature Tp is introduced into phase equilibrium relations to allow phase appearance and disappearance through the same governing equations. equilibrium relations. which carry out phase identiﬁcation and solution of governing equations simultaneously. Georgoulaki and Korchinsky reported that the number of iterations required by the Newton method (in the Napthali – Sandholm algorithm) was quite large and further improvements are necessary. In the ﬁrst method. 1996. heat duty and pressure speciﬁed) ﬂashes. Han (1996) proposed two equation-solving methods for multiphase equilibrium calculations. Shyamsundar. Both the methods of Cairns and Furzer (1990a) and Georgoulaki and Korchinsky (1997) require an explicit stability test in each iteration.j. 1). In the second method. Gupta. For checking the stability of the liquid phase.24
V. The method involves the solution of an optimization problem to perform phase identiﬁcation and solution of the governing equations simultaneously. 1997). The phase stability test proposed by Pham and Doherty (1990) was used. 1998). and the success of the proposed method was shown on several examples for three-phase distillation (Cairns & Furzer. and c components in the feed. and two immiscible liquids with ﬂow rates L I and L II and compositions x I and x II respectively (Fig. 1. G. each of which can be simulated by methods for phase equilibrium calculations (or temperature and pressure speciﬁed ﬂashes).
.j Temperature. with reboiler (as stage 1) and total condenser (as stage N). in which the phase equilibrium relations are relaxed by introducing a parameter k. Recently. A typical stage in three-phase distillation. This method simultaneously performs the phase identiﬁcation and calculation of phase quantities and composition at equilibrium. If the feed to stage n is absent.P. The method of Bullard and Biegler (1993) is not applicable to liquid–liquid equilibrium (LLE) calculations since LLE is almost independent of pressure. and it would also be difﬁcult to extend the formulation to multiphase systems.j n. are respectively T F. LLE and vapor–liquid–liquid equilibrium (VLLE) calculations via several examples (Han. Formulation of ®-method for three-phase distillation Consider a three-phase distillation column having N ideal stages. Application of this method to two and three-phase distillation simulation and optimization is studied here. Gopal and Biegler (1997) introduced a new method for multiphase equilibrium systems. which n are all speciﬁed. the tangent plane criterion of Michelsen (1982) was employed. Gupta (1990) proposed a method that uses stability variables to follow the appearance and disappearance of a phase on a stage during iterations. The three possible streams or phases (other than feed and product streams) leaving stage n (numbered from the bottom) are: a vapor with ﬂow rate V and composition yn. In the inner loop. especially near phase boundaries. from unity. The governing mass balances. 1990b). 1998).e. n. 2. namely. Gopal and Biegler (1997) used their method for dynamic simulation of multiphase ﬂashes. if any. ~-method (Han & Rangaiah.
Fig. Bishnoi and Kalogerakis (1991) have discussed potential numerical difﬁculties in the application of a similar method to phase equilibrium calculations. Cairns and Furzer (1990a) suggested a constrained version of the Napthali – Sandholm algorithm for simulating three-phase distillation. The efﬁcacy of the ~-method was shown for VLE. the phase fractions and stability variables are found while the phase compositions are updated in the outer loop. then Fn is zero. mole fraction summation of each phase is modiﬁed by introducing a phase characteristic variable. mole fraction summations and energy balances (MESH equations) for modeling three-phase distillation are as follows. if necessary. ~ to allow the summation to differ. Han & Rangaiah.j. Fn and zn. Rangaiah / Computers and Chemical Engineering 24 (2000) 23–37
culations. The resulting Tp-method was successful for both VLE and LLE problems (Han & Rangaiah. Multiphase distillation essentially consists of a series of Q –P (i. Potential of the method of Gopal and Biegler (1997) for simulation of multiphase distillation is also studied. Bullard and Biegler (1993) proposed a method for vapor– liquid equilibrium (VLE) calculations by introducing a pseudo pressure Pp to formulate
governing equations valid for different phase regions. The method was used successfully for simulating twophase distillation.

But it is not so since mole fraction summation is unity for existent phases. (5)– (7)) for each stage are modiﬁed to permit the summation to differ. (3) and (6)) are excluded from the governing equations. This modiﬁcation ensures that the governing equations are valid for a broader range of conditions. (for j=1. Whitson and Michelsen (1989) have developed negative ﬂash for VLE by allowing the vapor to feed ratio to exceed the physical limits of 0 to 1. Mass balances for reboiler (stage 1) L I +L II − V1 −L I −L II =0 2 2 1 1 L I x I j + L IIx II j −V1y1. respectively. For simulating three-phase distillation by the ~method. … . then the additional equations for the reboiler and condenser are as follows. that a (trial) phase is absent if its mole fraction summation is less than unity. yn. 1 1. It can be shown from the phase stability analysis in Michelsen (1982). otherwise. c)
(3) (4)
Mole fraction summations (for n = 1 to N) % yn.P. 2. j − L I x I j −L IIx II j =0 n n. N N. Shyamsundar. 2. …. n. …. Additional justiﬁcation for modifying mole fraction summation is presented in the appendix by considering the necessary conditions for the minimum of Gibbs free energy. but computational time for this is 50 to 200% more than that for the simulation based on real numbers.
j=1
c
Energy balances (for n=2 to N −1) Fnh F + Vn − 1Hn − 1 +L I + 1h I + 1 +L II+ 1h II+ 1 −VnHn n n n n n − L I h I −L IIh II =0 n n n n (8)
If the bottom product is taken as P1. (for j= 1. the top product in the form of liquid I and II is taken as P2I and P2II. several researchers have allowed a variable to take values beyond the physical limits (but mathematically valid) in order to overcome computational difﬁculties and develop elegant techniques. if necessary. if liquid I is absent at equilibrium. from unity by introducing a phase characteristic variable in each of them. … . j + Vn − 1yn − 1. In the past. c) (for j =1. Taylor. is extended in this study for simulating three-phase distillation without the a priori knowledge on phases and explicit phase stability test. Modiﬁcation of the mole fraction summation may appear contradictory to the conventional norm that mole fraction summation is equal to unity. and the modiﬁcation is only for nonexistent phases.
j=1
c
% x II j =1 n. 2. and the reﬂux ratio as R I and R II for liquid I and liquid II. j =1
j=1
(5) (6) (7)
% x I j =1 n.V. j +L II+ 1x II+ 1. c) (2) Equilibrium relations (for n =1 to N) yn. the corresponding equilibrium relations and mole fraction summations (Eqs. c) L I +L II − P1=0 1 1 Mass balances for condenser (stage N) VN − 1 − (L I +P2I)− (L II +P2II) =0 N N VN − 1yN − 1. j −(L I + P2I)x I j −(L II +P2II)x II j = 0 N N. G. which may improve convergence of the iterative methods used for
. 2 2. Thus different governing equations describe different phase regions. and the methods in literature for three-phase distillation simulation generally require a priori knowledge of the number and type of phases that exist at equilibrium on a stage. or an explicit phase stability test during the iterations. 2. The ~-method developed earlier for phase equilibrium calculations by modifying the mole fraction summation of a phase nonexistent at equilibrium (Han & Rangaiah. For example. j + L I + 1x I + 1. j −L I x I j −L IIx II j =0 2 2. 2. (for j=1. For example. …. j n n n n − Vnyn. n. j = K I j x I j n. 1 1. n n. Achuthan and Lucia (1996) have used complex domain calculations for two-phase distillation simulation. the three mole fraction summations (Eqs. c) L I − R IP2I =0 N L II − R IIP2II =0 N Energy balance for reboiler (stage 1) QR + L I h I + L IIh II − V1H1 −L I h I −L IIh II =0 2 2 2 2 1 1 1 1 Energy balance for condenser (stage N) QC +VN − 1HN − 1 − (L I +P2I)h I −(L II +P2II)h II = 0 N N N N (17) (16) (13) (14) (15) (12) (10) (11) (9)
The above equations for modeling three-phase distillation are valid only when all the three phases are present at equilibrium on stage n. 1998). respectively. (1991). and noted that complex calculations converge without difﬁculty to real solutions over a much wider range of speciﬁcations. j = K II j x II j n. Han and Rangaiah (1998) have proved through analysis and calculations that mole fraction summation of a nonexistent phase is less than unity. These equations can be modiﬁed suitably for other situations with regard to products. Similar conclusion can also be deduced from the equations in Gupta et al. Rangaiah / Computers and Chemical Engineering 24 (2000) 23–37
25
Mass balances (for n=2 to N −1) Fn + Vn − 1 + L I + 1 + L II+ 1 −Vn −L I −L II =0 n n n n Fnzn.
c
(1)
(for j =1. some of them are not applicable.

26
V. Vector. G. d is the search direction corresponding to variables in w. 1998): 1. These variables will eventually be reduced to zero at the minimum. The iterative algorithm for solving Eq. pm. j +~ V =1 n
j=1 c
of the optimization problem (Eq. L II. ~ I .P. ~ V. x II j. j. (21) by the ILP approach is as follows (Bullard & Biegler. Rangaiah / Computers and Chemical Engineering 24 (2000) 23–37
solving the equations. Tn. Shyamsundar. nm. Han & Rangaiah. and nm and pm are the non-negative artiﬁcial variables which ensure that the linear programming problem has a solution during the iterations (Bullard & Biegler. 2. Vn n n where
is a weighting parameter. Calculate hm (w k). The modiﬁed mole fraction summations are: % yn. yn. 1993). Select the tolerance m for convergence and a suitable value for
. n n n 05 L I . 1993. Set the iteration counter k to 0 and set initial values to w k. n
j=1
c
subject to hm + 9hmd= pm − nm 05 x I j. n. (21)) for the ILP approach is Minimize %
(~ V + ~ I + ~ II)+ % (pm + nm ) n n n
n=1 m N
(18) (19) (20)
(22)
% x I j +~ I =1 n. ~ II 5 1 n. 9hm and u k = N= 1
[(~ V)k + n n (~ I )k + (~ II)k]+ .

hm (w k).

Check whether convergence is achieved according to some criterion (here. S. using w k n n 3.

hm (w k).

stop./[(3c + 5)N +3]Bm was used). (22)). If converged. If . Else continue. 4. Find the search direction d k by solving the linear programming problem (Eq.

d k.

DD 5 N= 1
[(~ V)k + (~ I )k + (~ II)k]+ n n n n k m (pm + nm )− S. stop. continue. From the solution of the linear programming problem.B m. Else. ﬁnd the upper bound on the directional derivative at w k. 5.

hm (w ).

Set the step size. u= 1.. h(w N) and u N = N= 1
n [(~ V)N + (~ I )N + (~ II)N]+ S. Evaluate w N = w k + ud k. 6.

hm (w N).

(21) is equivalent to ﬁnding a three-phase solution. ~ I and ~ II are the phase characteristic varin n n ables respectively for vapor. and then go to step 6. Go to step 2. the maximum number of phases (namely. Vn. The linear form The ~-method for two-phase distillation was tested on two examples whose column details and speciﬁcations are summarized in Table 1. three) can be assumed on each stage at the beginning without a priori phase identiﬁcation. if there exists such a solution. …. (1). (1) – (4). all these equality constraints are represented by h(w) = 0. Tn. For the nonexistent phase.and three-phase regions on any stage. 2. (21) can be solved using nonlinear programming (NLP) or iterated linear programming (ILP) approaches (Bullard & Biegler. ~ I .r. ~ will be non-zero since mole fraction summation is less than 1. and the corresponding ﬂow rate must be zero which is ensured by Eq. x II j. In both
. Minimize % (~ V + ~ I +~ II) n n n
n=1 N
(21)
w. L II. x I j. Values of ~ V.t. are the modiﬁed MESH equations (Eqs. 8. respectively. j V n
[for m = 1. the modiﬁed MESH equations (Eqs. j II n. Tn N N In this problem. (8) – (20)). n n n 7.01u or − 0.
3. ~ I and ~ II are found by solving the n n n following optimization problem. ~ is zero and mole fraction summation is 1 consistent with the usual expectation. x . VN. The solvers OSL and CONOPT available in GAMS were used respectively for the ILP and the NLP approaches. The value of m and
used in this study is respectively 10 − 6 and 0. (8)–(20)) are valid for all single-. j. Else. yn. For the phase existing at equilibrium. then go to step 8. ~ V. For the application of ~-method to three-phase distillation.
% x II j +~ II = 1 n. n
j=1
c
where ~ V. equality constraints. ~ I and ~ II (for n n n. Set w k + 1 = w k + ud k and k= k+1. liquid I and liquid II on stage n. 1993). Effect of
on convergence was investigated on a few examples. yn. n n n n =1 to N and j =1 to c) subject to hm(w)=0
I n.5DDu 2/(u N − u k − DDu). With the replacement of Eqs. (18)–(20). (1) – (4). (5) – (7) by Eqs.5 unless otherwise stated. Maximum number of phases for application to two-phase distillation will be two. The problem in Eq. both were employed for solving this problem using GAMS. L II. Solution of the optimization problem 4. ~ .1uDD. two. Lower and upper bounds of ~ are 0 and 1. If u N − u k B 0. Example 1 was considered by Wu and Bishnoi (1986) and later by Gupta (1990) while example 2 was studied by Vasantharajan (1989) and later by Bullard and Biegler (1993). set u=maximum of 0. hm(w) where w is the vector of variables in the optimization problem. ~ II 51 n n 05 L I . In this study. (3c + 5)N + 3]
05 x . Application of ®-method to two-phase distillation The minimization problem in Eq. j.. n. L I .

Both ILP and NLP approaches were tried for simulating examples 1 and 2 by the ~-method. example 2 was simulated using the process ﬂowsheeting software. A two-phase ﬂash of the feed at the feed conditions and column pressure (which are all usually known) was performed by the ~-method (Han & Rangaiah.2201).3584 0. Liq. PRO/II. Results in Table 2 are comparable to these reported values.7724. the liquid phase was modeled by UNIQUAC model while the vapor phase by the virial equation for fugacity and enthalpy estimation.5 P1 = 61.1
Table 2 Selected results from the simulation of two-phase distillation: example 1 n 1 5 9 13 17 Tn 378.0043 0. 1998). 0 97. Minor differences in these proﬁles are possibly due to differences in the UNIQUAC interaction parameters and enthalpy data employed.V. Shyamsundar.2 620.P. Column pressure (bar) P =1. 0.. 0 15 40 5 20 20 Feed state Sat.7704 0.0079 0.000 Ln 45. (The ~-method gives composition of the two phases even if one of them is non-existent at equilibrium). To study the effect
on the convergence of ILP approach.1162 0.9 350.2 369.0 638.1870 0.0 0. The top most stage is the condenser with only a saturated liquid stream leaving the stage.5 560.7604 0.1444 0. 0. Hence.1888 0. the ILP approach was found to converge in ﬁve to six iterations. 0.9 kmol/h Feed stage =12
27
2
Liquid at 331.4 349. Wu and Bishnoi (1986) reported only component mole fractions in liquid on stages 1 and 17 as (0. Both the phase characteristic variables for vapour and liquid phases (~ V and ~ L) for all stages in examples 1 and 2. G.0076 2-Butanone 0.1.7723 n-Heptane 0. 0.9585. Similar consistent results were obtained for the steady state simulation and optimisation of two-phase distillation reported later in this paper.0041) and (0.6179 0.0237 0. while temperature on intermediate stages was estimated by linear interpolation of these two temperatures.8806 0. Bubble.9 357. similar to the procedure described by Haas (1992). each iteration is equivalent to one iteration of Newton method for solving nonlinear equations and involves the solution of an LP problem (see the algorithm in Section 3).0 604.1115 0. Rangaiah / Computers and Chemical Engineering 24 (2000) 23–37 Table 1 Details of two-phase distillation examples Example 1 (with two feeds) Components Toluene 2-Butanone n-Heptane Methanol Acetone Methyl acetate Benzene Chloroform Feed ﬂow rate (kmol/h) 45.6968 0.1 Vn 567.1959 0. For simulating two-phase distillation.0379 0. Sat. Liq.5 P1 =45 kmol/h Feed stages =10 and 6 N =17. R= 9.7699 0. Selected results from the simulation of example 1 by the ~-method are summarized in Table 2.2201
the examples.3 352.2363 0. Detailed results for example 2 are not available in Vasantharajan (1989) and Bullard and Biegler (1993). for comparison. R= 1.1603 0.0901 0. CPU time for examples 1 and 2 by ILP approach is respectively 18 and 37 s on a Pentium
. several values in the range of 1000 to 10 − 6 were tried for example 2.4 373. and the resultant phase compositions were used to initialize corresponding phase compositions on all stages.0314 0.7798 0.0342 0.0374. The results show that the number of iterations for convergence is unaffected for
in the range 1000 to 0. 97 55. Proﬁles of stage
temperature and phase ﬂow rates obtained by ~-method and PRO/II are compared in Fig.0075.0693 0.9 612.9578 0.0033 0.and dew-point temperatures of the feed were used to estimate reboiler and condenser temperatures.54K PC =1. were found to be zero since both vapour and liquid phases are present on each stage.7655 0.013 Column speciﬁcations N =17.5 Phase composition y x y x y x y x y x Toluene 0. Vapor and liquid ﬂow rates on all stages were initialized assuming reﬂux ratio (often given) and constant molar overﬂow. 2. and hence ~ V is zero and this stage temperature is the dew-point temperature of the entering vapour stream. respectively.015 PR =1.

j xn. the ILP approach generally requires less computational effort. Examples 1 and 2 were simulated using the same initialization (i. nm. j + yn − 1. yn. j xn. j n Eqs. Thus.
subject to hm = pm −nm 05 xn. was found to be the same as that for simulating columns with ideal stages.2.e.6 and was used for all stages in the simulation of two-phase distillation with non-ideal stages although different values can also be used. G. The total number of non-ideal stages thus obtained for both examples 1 and 2 is 29. Rangaiah / Computers and Chemical Engineering 24 (2000) 23–37
166 MHz personal computer. and then the two numbers are added. (26). j (pn − 1)= 0 (26) For the simulation of distillation with nonideal stages. For determining the total number of non-ideal stages in examples 1 and 2 (Table 1). Product compositions obtained in these simulations were comparable to those obtained earlier assuming ideal stages for the speciﬁcations in Table 1. This is not unexpected since the column speciﬁcations are the same and number of stages is modiﬁed for non-ideality. Number of iterations for convergence of the ~-method (with ILP approach) for simulating distillation columns with non-ideal stages. (24) and (25) can be combined to obtain yn. The corresponding values for NLP approach are 660 and 163 s. and the feed stages are 17 and 10 for example 1 (with two feeds) and 20 for example 2. 2.j) n. the number of ideal stages below (and including the) feed stage and above the feed stage is divided by the stage efﬁciency. This nonlinearity is perhaps of less importance because of many other nonlinear equations in the model.
The simultaneous simulation and optimization of operating conditions of two-phase distillation processes
.28
V. equilibrium relations in the MESH equations are replaced by Eq.1.j composition in equilibrium with xn.j : y*. Shyamsundar. Tn Example 1 was solved again via this formulation and CONOPT solver. taking initial values of pm and nm = 0. Simulation of two-phase distillation with nonideal stages
Since stages in a practical distillation column are not ideal. The results are
4. j. ~ L. vapor and liquid ﬂow rates in two-phase distillation example 2 (continuous line ~-method.j)/(y* − yn − 1. examples 1 and 2 were simulated by introducing Murphree stage efﬁciency given by pn = (yn. The CPU time for convergence of NLP reduced from 660 to 180 s. Typical value for stage efﬁciency is 0. dashed line: PRO/II).j − yn − 1. based on two-phase ﬂash of the feed) and the ILP approach. j. Simultaneous simulation and optimization
Fig. (25)
4. Temperature. The NLP in this formulation is: Minimize %
(~ V +~ L) + % (pm +nm ) n n
n=1 m N
(23)
the same as those obtained by the ~-method. Vn. Examples 1 and 2 were also solved using the kmethod of Gopal and Biegler (1997) along with the same initialization scheme based on two-phase ﬂash of the feed and using the ILP approach. ~ V 51 n n 05 Ln.j (24) where pn is the efﬁciency of stage n and y* is the vapor n.P. In order to improve the performance of NLP approach using CONOPT solver. pm. The number of iterations for the convergence of the kmethod and the ~-method (with the ILP approach) is also the same. j = Kn. j − pnKn. the optimization problem in the ~-method was formulated as NLP with artiﬁcial variables pm and nm in the equality constraints (as in the ILP approach). This is despite the fact that the kparameter introduced in the equilibrium relations in the method of Gopal and Biegler (1997) occurs nonlinearly while the ~-parameter in the modiﬁed mole fraction summations in the ~-method occurs linearly.

972 HKR 18. A three-phase ﬂash of the feed at the feed condition and column pressure was performed. The last term in the objective function is for minimizing the phase characteristic variables in the ~-method. only the NLP approach is appropriate for solving the optimization problem. A simultaneous simulation and optimization of two-phase distillation by the ~-method was tried by considering example 2.013 bar. The initialization was based on two-phase ﬂash of the feed (used earlier for simulation alone).02 is equally distributed among the other components). These improvements are achieved mainly by decreasing the reﬂux ratio from the speciﬁed value of 9.701 17. respectively. Example 4 is an extractive distillation considered by Buzzi Ferraris and Morbidelli (1982). 0. MESH equations) are nonlinear. The value of
is 0.829 LKC 14. LKC and HKR are the light and heavy key component ﬂow rates in the top and bottom products. (27)) is nonlinear. the objective function decreases by about 18% (Table 3).531 kmol/h. The results of simultaneously simulating and optimizing example 2 are summarized in Table 3 along with those obtained by simulation alone.7
29
is a nonlinear programming problem since the objective function and the constraints (i. For simulating the columns by the ~method. Eckert. the ﬁrst two terms in the objective function try to maximize LKC and HKR while minimizing the heat duties. 2 and 4 were modeled by the NRTL model. Column speciﬁcations for all the examples are summarized in Table 4. Hsieh and O’Connell (1980) was used for the second liquid phase composition (namely. In all the examples. Grens.5. Examples 1 and 2 were taken from Gupta (1990). Bubble.972
.108 14. The objective function is = 3. The results obtained for example 2 by the ~-method match with those reported in Vasantharajan (1989). the heat duties of the reboiler and condenser decrease by a factor of 3 compared to the simulation results.7 s on a VAX6320 using reduced SQP. G. For examples 2 and 4. and the constraints are the same as those in the simulation. For the same optimization problem. Example 2 was optimized for the column details given in Table 1 except that reﬂux ratio and bottom ﬂow rate. Rangaiah / Computers and Chemical Engineering 24 (2000) 23–37 Table 3 Simulation and optimization of two-phase distillation: example 2 Case Simulation Optimization −25. (27) is considered instead of that in Eq. For this.3×107 4. Anderson. the ﬂash gave the composition of only one liquid phase. Vasantharajan (1989) presented an algorithm based on the range and null space decomposition strategies for sequential quadratic programming (SQP) and compared it with MINOS algorithm for two-phase distillation optimization and other applications. vapor and liquid ﬂow rates on all stages were initialized assuming reﬂux ratio and constant molar overﬂow. while temperature of interme-
Here Q is the heat duty with the subscripts C and R referring to the condenser and reboiler. Shyamsundar.2 in the optimization. Example 3 is an 11-stage azeotropic distillation column studied by Cairns and Furzer (1990b) and Georgoulaki and Korchinsky (1997).2 P1 61.98 for the predominant component and 0. Since the objective function (Eq. however.9 56.5×106 QC −1.and dew-point temperatures of the feed were used to initialize reboiler and condenser temperatures. Vasantharajan (1989) reported a CPU time of 466. These two terms are the same as those used by Lucia and Kumar (1988) and Vasantharajan (1989). 1989). respectively. CONOPT solver in the GAMS was employed in the present study. The two liquid phases in examples 1. Application of ®-method to three-phase distillation Four examples were selected from the literature for the application of ~-method to three-phase distillation simulation. In effect. CPU time for optimizing example 2 by the ~-method using CONOPT is 660 s (on a Pentium 166).4×106 R 9. The optimization of the column results in the recovery of methanol increasing to 14. which had speciﬁc values in the earlier simulation are the (additional) variables for optimization. For optimizing the distillation columns by the ~method.P. same as that generally used in the simulation. (21) for simulation alone.e.3×107 −4. Lucia and Kumar (1988) applied a method known as thermodynamically constrained hybrid method for the optimization of distillation columns.0×10 − 7(QR − QC) −(LKC +HKR) + %
(~ V + ~ L) n n
n=1 N
kmol/h while the chloroform recovery decreases to 17. which is a very difﬁcult problem (Vasantharajan. and so the initialization suggested by Prausnitz.218 −29.5 in the simulation to 2.531 QR 1. the column pressure is 1. while the UNIFAC model was used for the liquid phases in example 3.
(27)
5. pressure drop in the column is negligible and the vapor phase was considered as ideal.5 2. Overall. the objective function in Eq. and the resultant phase compositions were used to initialize corresponding phase compositions on all stages.V.

0 P1 =34 kmol/h N =11 R I =2.Acrylonitrile =0..0127.0001 on stages 2 to 6. same as that reported by Gupta (1990). Simulation by the ~-method gave the same phase pattern. This simple initialization was successful for examples 2 to 4 using ILP approach. 3 and 4 as well as in Tables 5 and 6. which implies that the second liquid phase is absent on these stages. and is conﬁrmed by the existence of the second liquid phase on stage 7. 30 40 35 25 Feed condition Liquid at 363. composition of both the liquid phases is identical (e.. and hence ~ V is zero for all these stages. and the corresponding mole fraction summations are also less than unity. Shyamsundar.8K
7. which essentially indicates a single liquid phase. 0.30
V.9977. G. This decreasing trend of ~ II indicates that the second liquid phase may form on subsequent stages. Gupta (1990) reported two liquid phases on stages 1 to 6. A similar initialization scheme was utilized by Gupta (1990). When two liquid phases are present on a stage.0. Liq. and hence ~ V is zero and the stage temperature is the dew point of the entering vapor stream. 0.
Fig.0 6. Vapor phase exists on all other stages in the column. Temperature.0019. Rangaiah / Computers and Chemical Engineering 24 (2000) 23–37
Table 4 Details of three-phase distillation examples Example 1 Components Water n Propanol n Butanol Water Butyl acetate n-Butanol Acetone Chloroform Water Acrylonitrile Acetonitrile Water Feed ﬂow rate (kmol/h) 32.06 xI 18. R II =2.0023). and only one liquid phase on stages 7 to 12. vapor and liquid ﬂow rates in three-phase distillation example 1 [continuous line: ~-method. Only ~ II for stage 7 is found to be non-zero (0.g. These results are as expected for the ~-method.6 kmol/h.5. T F =344. and for all examples using NLP. Similar comments are applicable to results for example 2 in Fig. 8
4
7
diate stages was assumed based on linear interpolation of these two temperatures. 11 and 12 in Table 5). Stage 12 is the condenser with only a saturated liquid stream leaving the stage. R II =3.5 11.
.0 P1 =21 kmol/h N =7 R I =1. x II in Table 6 for stages 3 and 5 refers to the non-existent phase. stages 9.0003 and 0.05 P2 (aqueous phase) = 5
2
Saturated liquid
6
3 (with two feeds)
Sat.5 P1 =120 kmol/h N =18 xI 1. ~ V. Better initialization for these cases was provided by ﬁrst solving the problem as two-phase distillation and then ﬂashing the liquid on each stage for estimating the composition of two liquid phases. and are comparable to those reported by Gupta (1990). respectively. 3. 0. 10 20. R II =0. Also.35 K Feed stage 8 Column speciﬁcations N = 12 R I =3. In the latter case. If only one liquid phase is present on a stage.P. ~ I and ~ II for all stages are zero except ~ II = 0.0914. and hence x II for n =7 in Table 5 refers to the non-existent phase and the corresponding mole fraction summation is 0. Note that phase compositions for non-existent phase by the ~-method and those obtained by Gupta (1990) in Tables 5 and 6 can not be compared since the formulation in the two methods is different.5 16 23 11 60. ~ I and ~ II are zero. Results for examples 1 and 2 are presented in Figs.0. For example 1.Acetonitrile =0. Second liquid phase exists only on stage 7
(condenser) in example 2 and its ﬂow rate is found to be 11. 20 20. dashed line: Gupta (1990)]. But it failed for example 1 using ILP. either ~ for the non-existent phase is non-zero and the phase ﬂow rate is zero or both ~ and phase ﬂow rate are zero. 4 and Table 6. and the two stream ﬂow rates are non-zero. Sat Vap.

7381 0.6444 0.1992 0.P.2953 0.1472 0.9715 0. 0.7014 0.0343 0.1498 0.0194.
Results for example 3 obtained by the ~-method are presented in Table 7.3521 0.1512 0.1986 0.2019 0.9169 0. and any discrepancy in these data could lead to the differences in Fig.0701 0. G.0790 0.0603 0.5946 0.0719 0.0248
3
5
7
9
11
12
.0581 0. When the vapor phase and two liquid phases are present on a stage.3544 0.6467 0.2953 0. If only one liquid phase is present on a stage.1474 0. Both ILP and NLP approaches were tried for simulating all the four examples for three-phase distillation by the ~-method. Shyamsundar.0233 0.9637 0. composition of both the liquid phases is identical (e.2952 0.6174 0. 5 and Table 8. 4.1962 0.0404 0.0603 0.7188 0.9120 0. Rangaiah / Computers and Chemical Engineering 24 (2000) 23–37
31
Fig. This publication does not include references for the thermodynamic data used.9637 0.3868 0.0142 0.1085 0.0258 0.6935 0.2682 0.1356 0.2504 0.0015.6444 0.6141 0. Values of ~ II on stages 10 to 13 are respectively 0.0064 0.6789 0.7505 0.2964 0.0315 0.6618 0. The results show that
Table 5 Equilibrium phase compositions on selected stages in example 1: (1) this work and (2) Gupta (1990) n Phase composition Water (1) 1 y xI x II y xI x II y xI x II y xI x II y xI x II y xI x II y xI x II 0.7416 0.6911 0.3909 0.1980 0.1962 0.0423 0.0305 0.1314 0. vapor and liquid ﬂow rates in three-phase distillation example 2 [continuous line: ~-method.0384 0.8555 0.2072 0.7391 0.1121 0. Vapor and liquid phase compositions.7197 0.6917 0.1121 0.7054 0. ~ V.3521 0. agree well with those in Buzzi Ferraris and Morbidelli (1982).9500 0. either ~ for the non-existent phase is non-zero and the phase ﬂow rate is zero or both ~ and phase ﬂow rate are zero.6825 n-Propanol (1) 0.0514 0.0213 0.0247 0.0068 0.6624 0.1012 0.3544 0.1780 0. and the three stream ﬂow rates are non-zero.6898 0. In the latter case.1447 0.0135. To study the effect of
in the ILP approach.0662 0.0744 0.5989 0. ~ V. several values in the range of 1000 to 10 − 6 were tried for examples 1 and 3. 5 and Table 8. The phase pattern is correctly predicted with two liquid phases on all the trays.2678 0.0319 0.7019 0.0073 and 0.1110 0.7053 0.0412 0. Simulation by the ~-method gave the same phase pattern.2180 0.0130 0.0221 0.V. and stage temperatures for example 4 presented in Fig.6578 0. stages 1 to 9 in Table 8) which essentially indicates a single liquid phase.6174 0. ~ I and ~ II are zero.2998 0.0512 0.0995 0. and this decreasing trend is consistent with the existence of the second liquid phase on subsequent stages.0145 0.9493 0.2927 n-Butanol (1) 0.0315 (2) 0.0315 0.6599 0.3544 (2) 0.6795 0. Temperature.2030 0.9719 0.7520 0.1829 0. 0.0828 0.0305 0.0253 0.6141 0.0249 0. and only one liquid phase on stages 1 to 13 for example 4.1070 0.1040 0.1946 0. and the present results agree well with these (Table 7). dashed line: Gupta (1990)]. Buzzi Ferraris and Morbidelli (1982) reported two liquid phases on stages 14 to 18.g.1435 0.6141 (2) 0. Only values of the average mole fraction (of the liquid
phases) are available in Georgoulaki and Korchinsky (1997) for comparison.0226 0.0450 0. ~ I and ~ II for all stages in this column are zero.0137 0.0433 0.6917 0.2549 0.

7010 0.4805 0.0042 0.2012 0. Simulation of three-phase distillation with nonideal stages
Examples 2 and 3 were simulated by introducing Murphree stage efﬁciency as per Eq.6996 0.48 na 0.0916 0.0 0.
= 0.19
a
Note: x denotes average liquid composition. and vapor and liquid compositions on selected stages in example 3: (1) this work and (2) Georgoulaki and Korchinsky (1997)a Acetone n 1 3 5 7 9 11 Tn 333.2694 0.0922 0.1 75.28 na 0.0041 0.0051 0.4597 0.3314 0.0041 (2) 0. and the corresponding CPU times are 6.2001 0.23 na 0.1865 0.20 na 0.9862 Butyl acetate (1) 0.5 and 28.5 s.0992 0. 35 and 40 s (on a Pentium 166). vapor and liquid ﬂow rates.4644 0.1940 0. G.2026 0.9744 0.5110 0.3 s.2170 0.5 was employed.2730 0.9872 0. 8.2724 0. and it required better initialization for example 1.2060 0.48 na 0. The number of iterations for convergence of the k-method and the ~-method (with the ILP approach) is nearly the same.3 11. 2 and 4.2933 0. taking initial values of pm and nm = 0. 0. (24) which can be rearranged as:
.4650 0.4804 0.6 L II n 101.9 333. Since NLP approach (with CONOPT solver) failed to converge for example 3.4245 (2) na 0.0084 0.0916 0.2200 0.2860 0.1917 0.8 333.0911 0. Shyamsundar. NLP was successful for examples 1.20 na 0. The results are the same as those obtained by the ~-method.2929 0.2024 0.5352 0.4810 0. 17.2731 0. 5 and 10 for examples 1 to 4.3964 0.3174 0.4578 0.0087 0. Hence.6 11.35 na 0.3092 0. Rangaiah / Computers and Chemical Engineering 24 (2000) 23–37
Table 6 Equilibrium phase compositions on selected stages in example 2: (1) this work and (2) Gupta (1990) n Phase composition Water (1) 1 y xI x II y xI x II y xI x II y xI x II 0.3023 0.2268 0.2933 0.0976 0.0053 0.2860 0.5389 0.4656 0.0964 0.6970 0.38 Water (1) 0. and the corresponding CPU times are 2. respectively.7040 0.35 na 0.5105 0.9848 0.2263 0. and the CONOPT converged successfully and the CPU time needed is 2.6 4.2 93.1942 0.5 192. The initialization was based on the two-phase distillation simulation as before for the NLP.1 84.3082 0.2336 0.48 na 0.0049 n-Butanol (1) 0.6155 0. only when better initial values for variables (based on two-phase distillation simulation) are provided.2335 0.32
V.5 95.0094 0.9 333. Example 3 was tried
via this formulation (and CONOPT solver as before).2330 0.P.
5.2929 0.1918 0.0099 0.1940 (2) na 0.28 na 0.1999 0.2108 0.3024 0.1.1918 0.44 na 0.1918 0. ¯
number of iterations for convergence of ILP is almost unaffected for a wide range of
and that the number of iterations begin to increase when
is less than 0. Number of iterations for convergence is 2.4 140.3 Phase composition y x ¯ y x ¯ y x ¯ y x ¯ y x ¯ y x ¯ (1) 0.1.0083 (2) 0.1938 0.7079 0.2194 0.7 Vn 84.9 333.9 333.3 11.8 6.3610 0.6156 0.4094 0.3209 0.1872 0.6156 0.3192 0.1006 0.7 192.5358 0.3725 0.4452 0.6155 0. the optimization problem in the ~-method was formulated as NLP with artiﬁcial variables pm and nm in the equality constraints (as in the ILP approach).2015 0.5350 0.1 84.4420 0.3520 0.001 or greater than 20.9876 (2) 0.0911 0.2860 0.3815 (2) na 0. Examples 1 to 4 were also solved using the k-method of Gopal and Biegler (1997) along with the same initialization scheme as used for the ~-method and using the ILP approach.44 na 0.23 na 0.0959 0.4336 0.42 Chloroform (1) 0.0 LI n 18. in all applications.8 192. ILP was successful in simulating examples 2 to 4 starting from the simple initialization based on feed.28 na 0.7009 0.4608 0.23 na 0.9855 0.0088
3
5
7
Table 7 Temperature.

The objective of the optimization is to reduce the reboiler and condenser heat duties while trying to improve the recovery of light key and heavy key. (21) for simulation alone. (28) – (30). y*. optimization results in recovery of water decreasing to 4. leading to an overall performance improvement of about 80%. CPU time for the optimization of two examples studied is 20 s or less. which had speciﬁc values in the earlier simulation. Temperature. j − pny*. respectively.j is the vapor composition n in equilibrium with x I and x II : n. Rangaiah / Computers and Chemical Engineering 24 (2000) 23–37
33
yn. j +yn − 1. similar to that for two-phase distillation optimization (Section 4. Two types of initialization were tried for optimization: (1) using the results obtained earlier for simulation of three-phase distillation. j (pn −1) =0 n
(28)
5. Number of iterations for convergence of the ~-method (with ILP approach) for simulating distillation columns with nonideal stages is 9 and 5 for examples 2 and 3. G. In any case.8× 105 and −2. (3) and (4)) in the MESH equations are replaced by Eqs. n. 5.
(31)
Fig.j y* j = K I j x I j n. Optimization of the column in example 2 results in the recovery of water decreasing to 7. respectively.356 kmol/h. For example 3. dashed line: Buzzi Ferraris and Morbidelli (1982)]. stage efﬁciency. while the heat duty of the reboiler and condenser decreases by about half. Shyamsundar. and 12 and 13 for example 3. is also shown in Table 9. The heat duties of the reboiler and condenser decrease to 2. Eq.621 kmol/h while the chloroform recovery increasing to 29. equilibrium relations (Eqs. vapor and liquid ﬂow rates in three-phase distillation example 4 [continuous line: ~-method.368 kmol/h and the butyl acetate recovery increasing slightly to 21. Examples 2 and 3 were optimized for the column details given in Table 4 except that reﬂux ratios and bottom ﬂow rate. The total number of nonideal stages estimated by the procedure described in Section 4. n. The results of optimizing examples 2 and 3 are summarized in Table 9 along with those obtained by simulation alone.232 kmol/h. Overall. (31) is the objective function instead of Eq. was tried by considering the following objective function. and are comparable to those for the simulation assuming ideal stages. y*. and the feed stage is 10 for example 2. Optimization understandably requires greater computational effort than simulation only.
.P.6 although different values can also be used.1× 106 kJ/h.2). = 3.1.2. Product compositions obtained in these simulations are very close to those obtained earlier assuming ideal stages for the speciﬁcations in Table 4. This second type of initialization was used earlier for threephase distillation simulation by the ~-method in conjunction with the NLP approach. As before. CPU time (on a Pentium 166) for simulating and optimizing examples 2 and 3 by the ~-method with NLP approach (employing CONOPT). are the (additional) variables for optimization.V. Examples 2 and 3 were simulated using the simple initialization (based on three-phase ﬂash of the feed) and the ILP approach. Simultaneous simulation and optimization
A simultaneous simulation and optimization of threephase distillation by the ~-method. and (2) using the results obtained by simulating as a two-phase distillation followed by ﬂashing the liquid on each stage.j n.0× 10 − 7(QR − QC)− 10 − 2(LKC + HKR) + %
(~ V + ~ I + ~ II) n n n
n=1 N
In three-phase distillation. the objective function decreases by 92%. pn was chosen as 0. j = K II j x II j n. n (29) (30)
For the simulation of distillation with nonideal stages.
For simultaneous simulation and optimization of threephase distillation by the ~-method. is 11 and 18 for examples 2 and 3. n. These results show that initialization of optimization based on three-phase distillation simulation requires less computations since the starting point is feasible and so extra computations for generating a feasible starting point are not needed. and the constraints are the same as those in the simulation.

1314 0.4×105 −4.5.6124 0.4285 0.2899 0.3063 0.2987 0.1713 0.0851 0. The MESH equations for distillation are modiﬁed by introducing a phase characteristic variable.2623 0.8199 0.5839 0.3122 0.0 40.3066 0.3040 0.1033 0.2911 0.5221 0. and column optimization.3119 0.8206 – 0. All computations were performed in GAMS along with OSL and CONOPT solvers respectively for the ILP and NLP approaches. The results obtained by the ~-method for distillation examples. if necessary. Examples selected include azeotropic and extractive distillation.5699 0.3377 0.6090 0.4 (3.3018 0.6714 0.1302 – 0.3068 0.621 HKR 20.1194 – 0.0683 0.2987 0.5185 0.0349 0.0 156.9367
3
5
7
9
11
13
15
18
Table 9 Results from simultaneous simulation and optimization of three-phase distillation Example 2 2 3 3 Case Simulation Optimization Simulation Optimization 0. Shyamsundar.2443 0.2041 0.760 4.2798 0.2666 – 0.0538 (2) 0.714 29.and three-phase distillation was studied by considering typical examples taken from the literature. R II 1.34
V.8988 0.3524 0. 9.3102 – 0.3063 0.8447 0. This modiﬁcation provides a set of governing equations valid for all possible phase regions in multiphase systems.1262 0.5412 0.2437 0.3066 – 0. 1998).5980 0.0093 Water (1) 0.2998 0.0 120.6020 0.8918 0.2997 0.1572 0. a simultaneous solution method for steady state simulation and optimization of multiphase distillation is developed based on an equation solving method for phase equilibrium calculations (Han & Rangaiah.2947 0.0348 0.0500 0.4890 – 0. ILP and NLP were tried for solving the optimization problem in the ~method. ideal and nonideal stages.368 7.1314 0.5×105 −4.0533 0.2802 0.0600 – 0.2095 – 0.6567 0.232 24.0680 0.0600 0. Effectiveness of the ~-method for two.2911 0.0 2.
.4254 0.2110 0.2938 0.4026 0.8×105 QC −8.
6.2420 0. 0.4479 0. from unity.5 0.6698 0.2897 0.1201 0.0255 0.3993 – 0.0913 0.2037 – 0.3037 – 0.4872 0.2957 0.1023 0.3016 0.2891 – 0.0540 Acetonitrile (1) 0.9211 0.0256 0. Hence.P.3911 0.3071 0.2902 0.3049 0.9210 0.3100 0.356 QR 9.2058 0.2 CPU time (s) 0.0803 – 0.25.2623 0.0 0. Conclusions In this study.7276 0.9370 (2) 0. were found to be consistent by analysis and by comparison to those in the literature.2627 0.3116 – 0.0.7258 0.1258 0.0 P1 34.5 3.6567 0.0567 0.0092 (2) 0.5661 – 0. Rangaiah / Computers and Chemical Engineering 24 (2000) 23–37
Table 8 Equilibrium phase compositions on selected stages in example 4: (1) this work and (2) Buzzi Ferraris and Morbidelli (1982) n Phase composition Acrylonitrile (1) 1 y xI x II y xI x II y xI x II y xI x II y xI x II y xI x II y xI x II y xI x II y xI x II 0. 0.4839 – 0.2646 0. Two approaches.4026 0.3885 – 0.1×106 R I.4508 0.3073 – 0.5699 0.0919 0.5376 0.6532 – 0.0468 0.3871 LKC 12.1556 0. ~ in the mole fraction summation of each phase on each stage in order to permit the summation to differ.6754 0.924 21.0182 1.6×106 −2.0810 0.3 20 (16)a
a CPU time is for the initialization based on simulation of two-phase distillation while that in brackets is for the initialization based on simulation of three-phase distillation.4872 0. G.4923 0.1201 0.0535 0.6702 0.3049 0.0529 0.3501 0.3019 0.33. 2.5840 0.0810 0.2×105 4.0)a 2.0600 0.3018 0.3069 0.8199 0.2110 0.88 7.1699 0.3013 – 0.0500 0.3116 0.7×105 2. pseudo solutions and nonsmooth problems are unlikely to occur and the
convergence of the numerical method used for solving the equations is likely to improve. on a personal computer.8×106 2.3405 0.2062 0.

(A8) can be rewritten in the familiar form xi2 = K 21xi1 i
21 i
i= 1. Comparison of Eq. 2. and n T is the total number of i moles of component i in the mixture. From the Gibbs– Duhem theorem. c. For the non-existent phase 3. 2. To develop the necessary conditions for the minimum. 3. xi1 = 1. form the Lagrange function by including multipliers. Simultaneous simulation and optimization of three-phase distillation has apparently not been attempted so far.V. Since xi1. 2. 2. the ILP approach often converges starting from a simple initialization based on known feed conditions and requires less than 10 iterations (similar to those in Newton method) for convergence. ii1 and ii2 are zero (for i= 1. (A5–A7) are for i =1. 2. the third term in Eq. assume that phases 1 and 2 exist while phase 3 is non-existent at equilibrium.
In the above equations.
DG if + RT ln fik + RT% % nik
k i
( ln fik + hi − iik =0 (nik (A5) (A6) (A7)
iik ] 0 iiknik = 0
along with Eqs. c
31 i i1
Appendix A. c from Eqs. (A5) for k= 1 and 3. hi for equality constraints (Eq. Equality in the above equations is valid. Optimization of the column can be performed along with simulation by simply including a suitable performance or cost function in the optimization problem of the ~-method. and according to Eq. Comparing Eq. 2. … . …. (Alternately. The ~-method has potential for simulation of coupled columns and for dynamic simulation of multiphase distillation columns. At equilibrium. ni3 = 0 and ii3 ] 0 for i=1.P. … . .. (A5) is zero. c (A12)
should be minimum subject to % nik − n T = 0 i
k=1 3
for i= 1. 2. For phases 1 and 2 assumed to exist.) The reasoning can be extended to modifying the mole fraction summation for each of the phases involved in the equation solving methods (and in MESH equations for distillation simulation). c. ni1 and ni2 are positive. Eq. … . c.
. (A7). as was done by Gopal and Biegler (1997) for multiphase equilibrium calculations. k=1. (A2) and (A3). (A11) when phase 3 is non-existent. (A6) and (A7). c
(A9)
where K = i1/i2. … . Eqs. (A5) for k=1 and 2. DG if is the free energy of formation of component i. G. 2. This inconsistency between the set of equations in the equation solving approach and the necessary conditions for Gibbs free energy minimum when phase 3 is non-existent.) at the minimum. The proposed ~method was able to carry out this easily. Thus. for example at the dew point and bubble point. is less than one minute on a Pentium 166. c
(A1)
where K = i1/i3.. can be resolved by modifying the mole fraction summation for phase 3 to xi3 5 1. Out of three potential phases. … . 2. On the other hand. gives fi3 ] fi1 i= 1. fi2 = fi1 i= 1. L= % % nik (DG if +RT ln fik ) + % hi % nik −n T i
k i i i
−% % iiknik
k i
(A4)
The necessary conditions for minimum are:
is included. modiﬁed mole fraction summations along with the equilibrium relations and mass balances will form the set of equations in the equation solving approach. 2. Rangaiah / Computers and Chemical Engineering 24 (2000) 23–37
35
For solving the optimization problem in the ~method for distillation calculations. at the minimum. 2. … .. nik is moles of component i in phase k. the CONOPT solver used in the NLP approach requires good initialization and relatively more computations. which is inconsistent with Eq. (A3)). In equation solving methods for three-phase equilibrium calculations. xi2 and xi3 are mole fractions. R is the gas constant. the equilibrium relation xi3 = K 31xi1 i i= 1. …. c (A8) If fik is given by Pxikik where xik and ik are respectively mole fraction and fugacity coefﬁcient of component i in phase k. Shyamsundar. summation of mole fractions obtained from equilibrium relations can still be kept equal to unity provided equilibrium relations are modiﬁed by incorporating a factor k. to accommodate any phase becoming non-existent at equilibrium. Gibbs free energy given by G = % % nik (DG if +RT ln fik )
k=1 i=1 3 c
(A10) (A11)
and xi3 ] K x
31 i
i= 1. 3
(A2) (A3)
and nik ]0
for i =1. Performance of the CONOPT solver may be improved by introducing artiﬁcial variables in the equality constraints in the optimization problem. Basis for modifying mole fraction summation Consider a mixture of c components at temperature T and pressure P on a stage in a three-phase distillation. xi2 = 1 and xi3 = 1 should also be satisﬁed. … . Computational time for simulation of distillation examples studied by the ~-method along with ILP approach. (A2)) and iik for inequality constraints (Eq. 2. fik is the fugacity of component i in phase k. c k =1.

B. I. Industrial Engineering Chemistry Research.j
zn. P.. B. 75. Gopal.j L I (L II ) n n LKC n N P2I (P2II) QC (QR) R R I (R II) TF n Vn w x I (x II ) n.. Rigorous distillation calculations. L. even if one or more phases are non-existent (i. University of Calgary. R. Cairns. (1997). Distillation design (pp. Thesis. Shyamsundar. 29.P.. Note that mole fraction summation is unity when the phase is existent and less than unity only when the phase is non-existent. American Institute of Chemical Engineers Journal. A. New York: McGraw-Hill. W. & Biegler. & Furzer. R. Han. The National University of Singapore.j
number of components search direction feed ﬂow rate for stage n in distillation (kmol/h) a vector function denoting the set of equality constraints enthalpy of vapor leaving stage n in distillation (kJ/kmol) ﬂow rate of heavy key component in the bottom product (kmol/h) number of iterations for convergence vapor–liquid I (II) equilibrium ratio for component j on stage n ﬂow rate of liquid I (II) leaving stage n in three-phase distillation (kmol/h) ﬂow rate of light key component in the top product (kmol/h) stage number from bottom (reboiler) total number of stages top product ﬂow rate of liquid I (II) in three-phase distillation (kmol/h) heat duty of condenser (reboiler) (kJ/ h) reﬂux ratio for liquid in two-phase distillation reﬂux ratio for liquid I (II) in threephase distillation temperature of feed entering stage n in multiphase distillation (K) ﬂow rate of vapor leaving stage n in multiphase distillation (kmol/h) vector of variables mole fraction of component j in liquid I (II) leaving stage n
References
Bullard. Transactions Institute of Chemical Engineers. K. 675 – 689. Multicomponent three-phase azeotropic distillation: modern thermodynamic models and multiple solutions. L. T. T. Notation
xn ¯
yn. In H. 1364– 1382. 29.36
V. Cairns. J. V. G. Methods for multiphase equilibrium calculations. G. 21. P. Appendix B. Haas. Computers & Chemical Engineering. I. An approximate mathematical model for three-phase multistage separators. Buzzi Ferraris. (1990b).
. & Biegler. & Korchinsky. (1997). M. & Kalogerakis.e. 135 – 211). 64. Iterated linear programming strategies for nonsmooth simulation: a penalty based method for vapor – liquid equilibrium application. L. Industrial Engineering Chemistry Research. (1982)..j y* n. Fluid Phase Equilibria. Georgoulaki. 28. Gupta.Eng. A. P. in different phase regions). 101 – 115. Thesis. A.. 1383 – 1395. (2)) simultaneously. (1996). (1990a). Gupta.. 49 – 55. G. 95 – 109. & Furzer. Kister. ~ II n n
average liquid phase composition leaving stage n in three-phase distillation mole fraction of component j in vapor leaving stage n mole fraction of component j in vapor in equilibrium with the liquid leaving stage n mole fraction of component j in feed entering stage n parameter in the method of Gopal and Biegler (1997) tolerance for convergence Murphree efﬁciency for stage n step length phase characteristic variable for vapor entering stage n in three-phase distillation phase characteristic variable for liquid I (II) leaving stage n weighting parameter for the phase characteristic variable ~ objective function for distillation optimization
c d Fn h(w) Hn HKR IT K I (K II ) n. (1991). Nonsmooth dynamic simulation with linear programming methods.D. (1990) Steady state simulation of chemical processes. Rangaiah / Computers and Chemical Engineering 24 (2000) 23–37
The above modiﬁcation of mole fraction summation is based on the necessary conditions for the minimum and the fact that nik will be zero for the non-existing phase. nik will have to be zero for the non-existent phase in order to satisfy the total mass balance (such as Eq. A.j n. 17. & Morbidelli.j n. Computers & Chemical Engineering. Z. As noted in Han and Rangaiah (1998). K. Ph. (1)) and component mass balances (such as Eq. J. Modiﬁcation of mole fraction summations (or equilibrium relations) is introduced so that the equations in the equation solving approach are valid and consistent with the necessary conditions for the free energy minimum. Simulation of heterogeneous azeotropic distillation. in which case moles of all components in that phase are zero and mole fractions are indeterminate. A. M. G.j Greek letters k m pn u ~V n ~ I . (1993). Multicomponent three-phase azeotropic distillation: phase-stability and phase-splitting algorithm. Bishnoi. A method for the simultaneous phase equilibria and stability calculations for multiphase reacting and non-reacting mixtures.. 65 – 89. N.. (1992).

. G. Design and synthesis of heterogeneous azeotropic distillation: heterogeneous phase diagrams.. Carnegie Mellon University. A. T. 1263–1266. (1980). Michelsen. Computers & Chemical Engineering. Anderson. Grens. & Michelsen. E. 21 – 40. G. Eckert. A. H. Thesis. Pham. 12. Whitson. Complex domain calculations. (1986). 897–911. 43. part I: stability and part II: phase-split calculations. Computer calculations for multicomponent 6apor – liquid and liquid – liquid equilibria. 9. H. M.V. Fluid Phase Equilibria. & Rangaiah. The isothermal ﬂash problem. (1998). A method for steady-state simulation of multistage separation columns involving nonideal systems. & Rangaiah. G. 22. 93 – 111. J. The negative ﬂash.
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