Computers & Chemical Enginewing, Vol. IO, No. 4, pp.

353-360, 1986
Printed in Great Britain. All nghts reserved Copyright 0

0098-1354/86 $3.00 + 0.00

1986 Pergamon Journals Ltd

A POWERFUL SOLUTION ALGORITHM FOR SINGLE-STAGE FLASH PROBLEMS

M. KINOSHITAt Department of Thermonuclear Fusion Research, Tokai-mura, Ibaraki Japan 3 19-I Atomic Energy Research Institute,

I, Japan

T. TAKAMATSU Department of Chemical Engineering, Kyoto University, Sakyo-ku, Kyoto 606, Japan 1985)

(Received 29 January 1985; revision received 23 August 1985; received for publication 22 November

Abstract-A powerful solution algorithm is proposed for single-stage, multicomponent, vapor-liquid equilibrium flash problems. The basic equations are treated in their primitive forms. The iteration variables are liquid mole fractions, and the functions to be zeroed are chosen so that the Jacobian matrix is diagonally dominant with diagonal elements close to unity in a wide range of practical conditions. The Jacobian matrix calculated at rather wild initial estimates of the iteration variables is used for all the iterations, In cases where the nonideality of the mixture is relatively low, convergence is achieved in less computing time by using the unit matrix for the Jacobian matrix. The algorithm can handle narrowboiling, wide-boiling and highly nonideal mixtures. Scope-The solution of the multicomponent, single-stage, vapor-liquid equilibrium flash problem is an important task in computer process calculations. The purpose of the present work is to propose a powerful algorithm for the solution. Boston and Britt [l] recently developed an attractive flash algorithm based on several related concepts which makes it superior to, and radically different from, conventional algorithms. They defined a set of new parameters and formulated working equations using these parameters. The new parameters were used as the iteration variables. A significant feature of their algorithm is that those iteration variables are chosen to be as independent as possible of temperature, phase flow rates and composition and of each other. AS a result, the iterative calculation is relatively insensitive to the initial estimates of temperature or pressure; and the initial estimates of vapor and liquid mole fractions are not needed to start the calculation. The Jacobian matrix is diagonally dominant and the order of magnitude of diagonal elements is unity. Hence, the Newton-Raphson method can be replaced by Broydens method [2] with no significant deterioration in convergence characteristics. In the present algorithm proposed, however, the above-mentioned feature of the Jacobian matrix is presented by using a way quite different from that used by Boston and Britt [l]. The introduction of new parameters and reformulation of the model equations are not required; the basic equations derived are treated in their primitive forms. The Jacobian matrix evaluated at rather wild initial values of the iteration variables is used for all the iterations, and neither the Newton-Raphson method nor Broydens method [2] is necessary. Furthermore, the use of the unit matrix for all the iterations is more efficient in many cases. Conclusions and Significance-The proposed algorithm is characterized by the following.

(1) It is assumed that liquid mole fractions are given as X,S. Their values are then recalculated by using the basic equations derived. The differences between the assumed and recalculated values of liquid mole fractions are regarded as the functions to be zeroed, fks. This specific concept presents a remarkable success. (2) The function f, varies almost linearly with x,, and it is not very strongly affected by X, s (k # n). AS a result, the Jacobian matrix is diagonally dominant with diagonal elements close to unity. These features are observed in a wide range of practical conditions. (3) The Jacobian matrix calculated at rather wild initial values of the iteration variables (x~s) is used for all the iterations. Even when the unit matrix is used for all the iterations, converged solutions are obtained with no damping factor. However, the use of the unit matrix sometimes results in many iterations and longer computing time in cases of nonideal mixtures. For ideal mixtures, it is remarkable that the use of the unit matrix can lead to fewer iterations. (4) In cases where the purity of a component in the feed mixture is very high, the Jacobian matrix is almost completely the unit matrix, regardless of the physical property of the mixture and types of flash problems. In cases of very narrow-boiling, ideal mixtures, the Jacobian matrix is almost completely the unit matrix. (5) In cases where equilibrium ratios are dependent on vapor composition, an inner iterative loop for convergence of y,s is needed. The convergence is achieved by using a similar concept, and the unit matrix is used for the Jacobian matrix in the inner loop except under very high pressure conditions. (6) The stability of the iterative calculation is relatively insensitive to the initial estimates of x,s or yks,

tTo

whom

all correspondence

should

be addressed. 353

354 and rather by adding (7) The (8) The

M. KINOSHITA and T. TAKAMATSU wild initial values are acceptable. The new values of the iteration variables are calculated simply the corrections to the old values. algorithm can handle narrow-boiling, wide-boiling and highly nonideal mixtures. algorithm is rather simple. The basic equations are used in their primitive forms, and no

introduction of new parameters is required. The authors feel that the concept applied in the present study can be applied to other unit operation models as well. In fact, similar concepts were used by Kinoshita et al. for stage separation processes such
as reactive distillation [3], three-phase distillation [4] and multistage water/hydrogen exchange columns [S]. The concept can deal with rather complex model equations which stem from the complicated process structure [S, 61 or the incorporation of chemical reactions [3,5, 61, tray efficiencies [6,7] and liquid-phase separation [4] (see the Appendix). Although similar concepts were already applied to these cases, mathematical features of the concept are first clarified in the present study. In addition, the abovementioned features are the most eminent in the present application.

PROPOSED

SOLUTION

ALGORITHM

independent

of y,s,

The multicomponent, single-stage, vapor-liquid equilibrium flash is depicted in Fig. 1. The basic equations are the following: phase equilibrium, yi=K,xi, enthalpy balance, FH,=(FV)h + VH+Q; (2) i=l,...,m; (1) 3. 4. 5.

(6)
is solved for T, and then yis are calculated from equation (1). In cases where Kis are dependent on y,s, equation (6) is solved for T and yis in a specific way, described later. Since xis, T and yis are known, molar enthalpies, h and H, are determined. The vapor flow rate V is determined from equation (2). Then, liquid mole fractions are recalculated from equation (3) as Xis (X,s are normalized to eliminate truncation errors).

component-material balance, Fz,=(FV)x,+ VK,x,, i = 1,. .,m; (3)

summation equations, m xx,=1

yi= 1.
Boston and Britt [l] described problems, listed in Table 1. six types

(5) of flash

In cases where the enthalpy balance is not incorporated, L and V are input variables and Steps 3 and 4 are skipped. The authors define the following functions to be zeroed:

fk=xlr-Xk,

k=l,...,

m-l.

(7)

The solution of the flash problem is then the solution of the following nonlinear simultaneous equations: .fi(x,,.,%-,)=o

First, it is assumed known. 1. 2.

that xl,s (k = 1, . . . , m - 1) are f,-,(x,,:..,xm-,)=o > .

(8) After the initial values of x,s are appropriately assumed, the new values of the iteration variables for the next iteration are calculated simply from x{+=xf+Axk, k=l,..., m-l. (9)

Then, x, is determined from equation (4). By the bubble-point calculation, T, K,s and y,s can be calculated. In cases where K,s are

v, Y, ,H
Table I. Types of single-stage, vapor-liquid eauilibrium flash oroblems Specified variables ;:, Calculated variables T, I v, P

Q. V
1

T, P
P, Q T. Q V, Q

V, T v, p T, P

L
Fig. 1. Schematic diagram

x, ,h
of a single-stage flash.

Specified C&Xl&d

Solution of single-stage flash problems The iterative once

m-l

355

calculation

is considered

converged

J=

1
k==l

]Q/(m-l)<C,

O<CC<l,

(10)

In cases where Kis are dependent on y,s, Step 2 requires a convergence calculation for yts whose concept is similar to that of the above-mentioned convergence calculation for xks. Assume that yks are known. Then, y,,, is determined from equation (5). 2. Equation (6) where y,s are substituted for Kis, is solved for T. 3 The vapor mole fractions are recalculated from equation (1) as Y,s. The functions to be zeroed, defined by
1.
gk=Ykyk>

is satisfied. The Jacobian matrix is expressed by

G= where

: .. af,_iiax,_, ..: I af,-;/ax,

afiiax,

. . ana+,

(11)

(12)
The partial derivatives in equation (1 l), elements of the Jacobian matrix, are numerically evaluated. The feature of the Jacobian matrix is that it is diagonally dominant and the diagonal elements are close to unity in a wide range of practical conditions. Hence, the Jacobian matrix evaluated at rather wild initial values of xks can be used for all the iterations. As proved in the numerical examples described later, the use of the unit matrix for all the iterations can be more efficient in many cases. Thus, neither the Newton-Raphson method nor Broydens method [2] is needed, and the main loop is a simple direct substitution, as illustrated in Fig. 2.

k=l,...,m-1,

(13)

are thus calculated. The converged solutions are found by solving the following nonlinear simultaneous equations: g,(Y,,...,Y,-,)=O (14) g,-,(Y,>:..,Y,_,)=o > .
most practical problems, the Jacobian matrix is strongly diagonally dominant and the diagonal elements are very close to unity. Hence, the unit matrix can be used for all the iterations in all the iterative loops:

AYyk =

-gk.

(15)

Calculate

from

equatlon110)

Yes

G
II

= Jacobian = Unit matru

matrix

= Column f, s

vector

of

= Column Xk s

vector

of

No

Fig. 2. Brief flow chart of the present algorithm. When the unit matrix is used in place of the Jacobian
matrix, the corrections are calculated simply from Ax, = -fk.

356

M.

KINOSHITA

and T.

TAKAMATSU

Under very high pressure conditions, however, the Jacobian matrix evaluated at rather wild initial values of yks in the first iterative loop is often more efficient, owing to the high vapor-phase nonideality. 3. Types II, IV and V The problems of these three types can be handled with minor modification of the above-described algorithm. In Type II problems, Step 2 in the liquid composition convergence loop is replaced by the solution of equation (6) for P (or P and y,s). In Type V problems, the phase flow rates are fixed, so Q is calculated from equation (2) after the liquid mole fractions are converged. Solution of Type IV problems is also straightforward. Type VI Assume that determined. Either x,s are known, and x, is also

and equation (20) is solved for T and P; and Y,s are calculated from equation (I). Again, equation (14) is solved in the specific way described above. Then, X,s are calculated from equation (19).

f, Vz,YW+
or i$, (FziKi)/(KiV

F - VI = 1

(16)

Thus, equation (8) is solved in accordance with the procedure described in Fig. 2. There is one thing to be noted here. Although the present algorithm may look similar to the WangHenke type method [8] when applied to Type I problems, it cannot be categorized as the WangHenke type method. It is true that temperature and phase flow rates are calculated from the equilibrium equations and the enthalpy balance, respectively. However, these calculations are made just in the process, and the calculated temperature and phase flow rates are never used as the iteration variables. All the basic equations are treated simultaneously in the algorithm. Thus, the algorithm is expected to handle both narrowand wide-boiling mixtures almost equally well.

NUMERICAL

EXAMPLES

+ F - V) = 1

(17)

is solved for V (or V and y,s). Equations (16) and (17) can readily be derived from equations (1), (3), (4) and (5). The use of equation (16) avoids the trivial solution V = F and the use of equation (17) assures a solution other than V = 0. When Kis are dependent on yis, the convergence of y,s is also required. This is achieved by using the specific way described above: y,s are used for calculating Kis and, after the convergence of V, Yis are determined from Y, = (FziKi)/(KiV Then, X,s are determined X, = (Fz,)/(K,V + F - V). from (19) (18)

To investigate features of the functions defined by equation (7), the two examples (Examples 1 and 2) summarized in Tables 2 and 3 are first considered. Binary mixtures are chosen because of readiness of graph plotting. Example 1 treats a wide-boiling, ideal mixture. Figure 3 shows the relation between x1 and fi which represents a nearly linear variation. Hence, an approximate solution is obtained in only a single iteration, regardless of the initial estimate for x,. Example 2 treats a relatively narrow-boiling, nonideal mixture. Figure 4 shows the relation between x1 and f,. Again, f, varies almost linearly with x, in a wide range of the x,-value, although this feature is not as prominent as in Example 1 owing to the relatively high nonideality.
10

+ F - V).

Thus, equation (8) is solved in accordance with the procedure described in Fig. 2. If necessary, Q is calculated from equation (2) after the convergence of x,s is achieved. Type III 1. 2. Assume that x,s are known, and x,,, is also determined. The following nonlinear simultaneous equations are solved for T and P (or T, P and y,s): i$, Y: = 1, Y: = KG, (20) FH,=(F-V)h+VH+Q I

.-0

Solution: x,* 0.9456

0.0

0.2

0.4

06

0.6

1.0

Independent variable, x, Fig. 3. Relation between x, and f, in Example 1. It is observed thatf, varies almost linearly with x, and the slope is approximately unity.

where H is calculated by using y*s. When Kg are dependent on y,s, the convergence of yks is also needed: y,s are used for calculating K,s

Solution of single-stage flash problems

357

As listed in Tables 2 and 3, 23 examples are further considered for ideal and nonideal mixtures. Examples 1, 3, 9, 10 and 11 treat ideal mixtures and nonideality is considered in the other examples. Wide-boiling mixtures are treated in Examples 1, 3, 19, 21-25. Example 11 assumes an extremely narrow-boiling mixture. Examples 5, 8 and 20 also act as extremely narrow-boiling mixtures because the feed mole fractions of all but one of the components are very small. Examples 14-18 are characterized by the high nonideality of the mixtures. In Examples 19-25, The vapor-liquid equilibrium ratios are dependent on vapor composition. High pressure is a feature of Examples 24 and 25. The initial values of .x,s are equal to zis in all the examples except Examples 22,24 and 25. The reason for assuming different initial values in these three examples is not that the stability of the proposed algorithm is significantly deteriorated but that there is no solution of the equation of state developed by Starling and Han [14, 151. In Examples 22, 24 and 25, the assumed initial values are (1 .OOE- 2, 9.43E - 1,

u ; s ._ t c a -0 2

-0

-1

o00 02 0.4 0.6 variable, 0.6 10 Independent

x,
in Example 2.

Fig.

4. Relation

between

x, and fi

2.70E -2, 7.40E - 3, 4.9E- 3, 2.00E- 3, 5.70E 3), (3.60E - 2, 9.34E - 1, 3.00E - 2) and (S.OOE- 2, 9.50E - l), respectively. In Examples 19-25, the vapor composition convergence loop is incorporated.

Table 2. Numerical

examples

tested Phvsical orooertv model Enthalpy Polynomial Polynomial Polynomial Polynomial in temperature in temperature in temperature in temperature [9] [9] [9] [9]

Example

Mixture Hypth.l-Hypth.2 Acetone-Methanol Hypth.l-Hypth.2-Hypth.3 Acetone-Methanol-Water

Type I
I I

Equilibrium Antoine equation [9] Antoine equation [9] Wilson equation [9) Antoine equation [9] Antoine equation 191 Wilson equation [9]

I I III VI VI I

5 6 7 8 9 IO I1 12 13 14 15 16 17 18 19

Acetone-Methanol-Water Acetone-Methanol-Water Acetone-Methanol-Water Acetone-Methanol-Water Hypth&Hypth.>Hypth.6 Hypth.4HypthS-Hypth.6 Hypth.7-Hypth.8-Hypth.9 Acetone-MethanolLEthanolL Water-Butanol Acetone-Methanol-EthanolWater-Butanol Water-Acetone-Furfural Water-Acetone-Furfural Acetone-Chloroform-Methanol Benzene-Ethanol-n-Hexane Benzene-Ethanol-n-Hexane Nitrogen-Methane-EthanePropane-n-Butane-n-Pentanee n-Hexane Nitrogen-Methane-EthanePropane-n-Butane-n-Pentanen-Hexane Nitrogen-Methane-Ethanee Propane-rr-Butane-n-Pentane n-Hexane Nitrogen-Methane-EthanePropane-n-Butane-n-Pentanen-Hexane Nitrogen-Methane-EthanePropane-?I-Butane-n-Pentanen-Hexane Hydrogen-Methane-Ethane Helium-Nitrogen
0.998,

Antoine

equation

[9]

Polynomial Polynomial Polynomial

in temperature in temperature in temperature

[9] [9] [IO]

I I I
II I VI I I VI I

Antoine equation [9] Antoine equation [IO] Wilson equation [IO]

Antoine equation [3] Wilson equation [3] Antoine equation [3] Wilson equation [3] Antoine equation [I I] Black 3 equation [12, 131 Equation of state developed by Starling -

and Han [14, 151

20

21

II

22

III

23

VI

24 25 tThe K-values
(0.975,

VI VI

Equation Equation

of state developed of state developed

by Starling by Starling

and Han [14, IS] and Han [14, I51 (0.0005, IO, I), (0.07, 4, 2) and

at the atmospheric pressure I .02), respectively.

of the three components

in Examples

3, 9 and 1 I are approx.

358

M.

KINOSHITA

and T.

TAKAMATSU

The initial values of yis are also equal to zis in all examples except the above three. The assumed initial values in the three examples are (5.00E - 2, 9SOE - 1, l.OOE - 3, l.OOE- 5, l.OOE- 6, l.OOE 7, l.OOE - 8), (7.00E - 1, 2.997E - 1, 3.00E - 4) and (9.50E - 1, 5.00E - 2), respectively. Thus, note that wild initial estimates are used in the present numerical experiments. Better initial values may readily be obtained, but those wild values are intentionally used to prove the powerfulness of the proposed algorithm. The new values of the iteration variables (xk s and yk s) are determined just by adding the corrections to the old values with no damping factor. The value oft in equation (10) is set at a suitably small value (= 5.OE - 6). The numerical experiments are performed in double precision by means of the FACOM M-380 system at the Japan Atomic Energy Research Institute. The numbers of total iterations needed are given in Table 4. It is remarkable that the converged solutions are obtained in all the examples considered even when the unit matrix is used for the Jacobian matrix for all the iterations. As mentioned before, and proved in Table 4, the use of the unit matrix in the vapor composition convergence loop results in no appreciable deterioration in convergence characteristics except in Example 24, which has the high vapor-phase nonideality. For the liquid composition convergence loop. use of the unit matrix in cases of nonideal mixtures sometimes results in many iterations and longer computing time. In cases of ideal

mixtures, however, it is interesting that use of the unit matrix can lead to fewer iterations.

Table 4. Numbers Example 8, 5 2 6 6

of total iterations Btb Y;

needed ytb

I
2 3 4 5 6 I 8 9 IO II I2 13 I4 IS I6 I7 I8 I9 20 21 22 23 24 1< ii

(;:
4 9 (15) 9

I
6 8

I
4

;
5

I
I 4 4 2 2 I 3 3 2 I 2 2 4 2 1 L 8 9 3 (i) 5 (8) \ 3 I 4 (Ii)
I

2 I 2 2 I 2 2

2 I 2 2 (i) 3

3 3

The Jacobian matrix evaluated at the initial values of the iteration variables is used for all the iterations. bathe unit matrix is used in place of the Jacobian matrix for all the iterations. Enclosure by parentheses means that use of the unit matrix results in longer computing time.

Table 3. Calculational Example I 2 3 4 5 6 7 8 9 10 II I2 I3 I4 I5 I6 I7 I8 I9 20 21 22 23 24 25

conditions

assumed

in the numerical H,(kJ/mol) 36.66 21.72 36.30 32.21 38.05 32.21 32.21 38.05 32.43 l9,48 35.51 20.66 20.66

examples Specified parameters Q Q Q Q Q Q = = = = = = 0.0, 0.0, 0.0, 0.0, 0.0, 0.0, P = I P= I P= I P= I P= I atm atm atm atm atm

Feed mole fractions (5.OE - I, 5.OE - I) (5.OE - I, 5.OE - I) (4.OE - I, 5.OE - I, I .OE - I) (3.OE - I, 3.OE - I, 4.OE - I) (l.OE-4, l.OE-4, 9.998E-I) (3.OE - I, 3.OE - I, 4.OE - I) (3.OE - I, 3.OE - I, 4.OE - I) (I .OE - 4, I .OE - 4, 9.998E - I) (3.OE - 1, 3.OE - I, 4.OE - I) (l.OE-4, 9.9988-I, l.OE-4) (3.OE - I, 3.OE - I, 4.OE - I) (2.OE-I,2.OE-1,2.OE-1,2.OE-I, 2.OE-I) (2.OE - I, 2.OE - I, 2.OE - I, 2.OE - I, 2.OE - I) (3.44E - 3, 9.816E - I, I .496E - 2) (3.44E - 3, 9.816E - I, 1.496B - 2) (3.OE-1,3.OE--1,4.OE-I) (5.OE - 2, l.OE - I, 8.5E - I) (5.OE - 2, l.OE - I, 8.5E - I) (1.4E - 2, 9.43E - I, 2.lE - 2, 7.4E - 3, 4.9E - 3, l.OE - 3, 2.7E ~ 3) (l.OE-4, 9.9948I, I.OE-4, l.OE-4, I .OE - 4, I .OE - 4, I .OE - 4) (1.4E-2, 9.438-1, 2.lE-2, 7.4E-3, 4.9E - 3, I .OE - 3, 2.7E - 3) (1.4E-22, 9.43EI, 2.7E-2, 7.4E-3, 4.9E - 3, I .OE - 3, 2.7E - 3) (1.4E-2, 9.43E-I. 2.7E-2, ?.4E-3, 4.9E - 3, l.OE - 3, 2.7E - 3) (3.6E- I, 6.lEI, 3.OE-2) (5.OE - I, 5.OE - I)

V/F = 0.7429 T=344.2 K, P = latm T = 373.1 K, P = I atm Q = 0.0, P = I atm

Q=-1256kJ/h, P=latm Q = 0.0, P = Iatm Q = 418.6 kJ/h, P = I atm Q = 418.6 kJ/h, T = 340.0 K P = I atm T = 330.6 K, P = I atm P = I atm P = I atm T = 337.8 K, P = I atm Q = -215.0 kJ/h, P = IOatm Q = -215.0 kJ/h, P = IOatm T= 150.0K

-7.734 - 7.285 - 7.734 -1.734 -7.734 - 1.272 -1.009

Q = -2l5.OkJ/h. Q = -215.0 kJ/h,

V/F = 0.2014

T=l58.9K, P = IO&m
T = 150.0 K, P = 35 atm T=80.0K, P =50atm

tThe feed flow rate is 100 mol/h in all the examples. The If,-value given for Examples 19-25 is the difference in the enthalpy of the compound at the specified temperature-pressure condition of the feed and the enthalpy of the compound in the ideal gas state at the same temperature.

Solution of single-stage flash problems

Table 5. Jacobian matrices evaluated at the initial values examples Jacobian I/ I/ /I 1.00 3.40E - 5 6.18E - 1 5.61E -2 Y.4lE - I .39E 1.22E 3.49E 2.32E 4.14E 1 -l.llE-6 of the iteration variables in some representative

359

Example 5 18 19

matrix

I .oo
3 -3.17E9.95E - I 6.25E 1.01 -1.25E-2 -3.68E - 2.4SE -5.OlE - 3

I/ II
6.858 9.89E 9.90E -2.98E - I .98E -4.05E 3 3

I I
2 2 3

I
3 3 4

II
25 (/ Jacobian matrix

- 3 - 3 - 4 2 3 5 7

7.888 9.658 - 1.08E 9.9lE - 2.06E -4.20E -4.838 4.67E 1.47E 1.00 8.858 4.56E

3 3 2 1 3 4

7.70E 8.61E -l.OlE-2 -2.87E 9.98E -3.88E

- 3 - 3 - 3 - I - 4 2 4 5 7

I .62E 2.86E - 2.77E -7.90E -5.258 9.99E

2 2 2 3 3

9.llE1 8.63E - 2 2.67E - 3 1.42E-4 1.63E-5 8.42E - 7 9.78E -

- 8.20E I .08 2.478 1.3lE-4 1.50E 7.14E -

-6.34E - 2 6.14E - 2 1.00 l.OlE-4 l.l6E-5 5.918 - 7

- 2 - 3 - 3 - 6 - 7

- 3.238 3.128-2 9.848 5.20E 1.00 3.06E -

-1.60E-2 a 1.55E - 2 4.9lE-4 2.60E - 5 2.96E - 6 1.00

11 9.68E

111 I (1 a
convergence loop.

in the vapor composition

Some representative Jacobian matrices calculated at the initial values of the iteration variables are given in Table 5. It is observed that the matrix is diagonally dominant and the diagonal elements are close to unity. Above all, in cases of very narrow-boiling, ideal mixtures, the matrix is almost completely the unit matrix. Also, in cases where the purity of a component in the feed mixture is very high, the matrix is almost completely the unit matrix, regardless of the physical property of the mixture and types of flash problems. In these special cases, ax,

y,s, r, L and V is tested in Example 10. Four iterations are needed to achieve convergence. When the Newton-Raphson method is replaced by Broydens method [2], seven iterations are needed. On the other hand, the present algorithm presents convergence in only a single iteration with the simple procedure of using the unit matrix in place of the Jacobian matrix.
Acknowledgements-The authors wish to express their sincere thanks to the reviewers who raised the quality of the present paper significantly.

ax,
F =

NOMENCLATURE

in equation (12) is nearly equal to zero; and the converged solutions are obtained in only a single iteration. The iteration histories in some representative examples are given in Table 6 for further information. For comparison, the global Newton-Raphson method linearizing the basic equations in terms of x,s,

Total molar flow rate of feed

Function Jacobian Function to be zeroed, defined by equation (7) matrix to be zeroed, defined by equation (13)

f= G = g = H = HF = h = J =

Molar enthalpy of vapor Molar enthalpy of feed

Molar enthalpy of liquid Average value of absolute of functions to be zeroed

Table 6. Iteration
Example B

histories

in some representative XS

examples J

5 18

0 I 0 I 2 3 0 I 2

I .OOE ~ 4 4.22E - 6 5.00E 2.26E 2.32E 2.328 2 2 2 2 2 3 3 3 3 3

I .OOE ~ 4 1.70E ~ 5 I .OOE I .04E I .04E 1.04E 9.43E 4.90E 9.40E 6.12E 9.40E 6.14E ~ ~ I 1 I I I 3 I 3 1 3 2.70E l.OOE 3.35E 1.25E 3.36E 1.25E 2 3 2 3 2 3

8.948 - 5 445E12 9.848 2.12E l.OlE 4.88E - 3 -4 - 5 - 7

19

I .4OE 7.40E 6.69E ~ 9.24E 6.71E 9.26E -

2.88E - 3 3.85E - 5 2.84E - 7 3.88E - 2 1.4lE-4 9.758 - 7

25

0 I 2

5.00E - 2 1.03E - 2 1.05E - 2

360

M. KINOSHITA and T. TAKAMA~U 15. K. E. Starling and M. S. Han, Hydrocarbon Process.

51(6), 107 (1972). 16. I. Suzuki, H. Yagi, H. Komatsu and M. Hirata J. them. Engng, Japan 4, 26 (1971).

K = Vapor-liquid equilibrium ratio L = Total molar flow rate of liquid m = No. of components P = Total pressure Q = Heat removal rate T = Absolute temperature V = Total moiar flow rate of vapor X = Recalculated value of liquid mole fraction x = Liquid mole fraction Y = Recalculated value of vapor mole fraction y = Vapor mole fraction z = Feed mole fraction
Greek symbols 8, = No. of total iterations needed in liquid composition

APPENDIX
Simulation of a Multistage Reactive Distillation Column

As a further example application, a reactive distillation column is simulated here by accounting for plate efficiencies [3,7]. Four components are processed and the reaction promoted is CH,COOH + C2HJOH+H20 + CH,COOC,H, The physical parameters needed in the simulation are given in Refs [3, 161.The calculational conditions assumed are the following: Total No. of plates = 20, Feed plate No. = 10, Feed composition = (5.OE - 1, 4.5E - 1, 5.OE - 2, 0.0) Feed temperature = 370.0 K (liquid), Feed flow rate = 6 mol/h, Flow rate of distillate = 1.2 mol/h, Reflux ratio = 10, Total condenser, Liquid holdup = 0.3 l/plate, 1.5 l/reboiler, Pressure = 1 atm, Plate efficiencies = 0.75 for all components. The iteration variables are liquid mole fractions. The top and bottom compositions are assumed to be (1 .OE - 6, 3.5E- 1, l.OE- 1, 5.5E - 1) and (4.OE- 1, 2.5E- 1, 2.5E - 1, l.OE - 1), respectively; and the other liquid mole fractions are calculated using the linear variation assumption. These are used as the initial estimates. The Jacobian matrix evaluated at the rather wild initial estimates is used for all the iterations. Thus, the calculation of the Jacobian matrix and its inversion are needed only once, and neither the Newton-Raphson method nor Broydens method is necessary. Nevertheless, the converged solutions are obtained in six iterations as explained in Table Al.
Table Al. Achievement of convergence in the simulation of a reactive distillation column accounting for plate efficiencies Iteration No. 0 Average value of the absolute of functions to be zeroed 492E 1.17E 3.03E 5.868 1.39E 3.2lE 7.53E 2 2 3 4 4 5 6

convergence loop y, = No. of total iterations needed in vapor composition convergence loop t = Convergence tolerance
Subscript p = Iteration number ( = 0, 1, Subscripts i = Component index ( = 1,

, b,)
, m)

k=Componentindex(=l,...,m-1) n = Component index

REFERENCES

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