Table 7 Extractive distillation with bromide RunNo.

FeedcomSaltcon-

reflux

containing Vaporcom-

zinc

agent, the methylene chloride content of acetone can

be reduced to 0.09 mole% or less.

position of
Nomenclature C = salt (wt%) in methylene chloride-acetone-salt liquid phase x1 = mole fraction ofmethylene chloride in liquid phase

position

mole% methylene chloride

12.00 5.35

centration

C [wt%]
0

mole% methylene chloride

abo ut 10 abo ut 30 abo ut 50 0 abo ut 10 abo ut 30 abo ut 50
6.50 4.55 4.50 1.75 0.72 0.41 2.75 0.31 0.ll 0.09
0 0

bottom product,

4.65 4.65 4.65 4.65 3.20

3.20 3.20 3.20

2/i = mole fraction of methylene chloride in vapor phase Literature cited

(salt-free

basis)

1) Dreisbach, R. R.: "Physical Properties of Chemical Compounds-II," American Chemical Society, Washing2) ton (1959) Hashitani, Kogaku, 32, 182 M., M. Hirata (1968) and Y. Hirose: Kagaku

10

Conclusions Vapor-liquid equilibrium data pressure of the system: methylene with zinc bromide, zinc chloride at atmospheric chloride-acetone and potassium

3) Hirose, Y. and M. lino: Preprint for the 33rd Annual Meeting of the Soc. of Chem. Engrs,Japan, p. 179 (1968) 4) 38, Johnson, A. I. and W. F. Furter: Can. J. Chem. Eng., 78 (1960)
5) Long, F.A. and W.F. McDevit:
(1952)

Chem. Rev.,

51, 119

thiocyanate are measured. The increase of relative volatility of methylene chloride at high acetone concentrations is noticed when zinc bromide is added in the methylene chloride-acetone mixtures. Moreover, the addition of zinc bromide is confirmed to eliminate the tangent azeotrope. By extractive distillation employing zinc bromide as separating

6) 44,Meranda, D. and W. F. Further: 298 (1966)

7) 9, Ramalho, R. S. and N. S. Edgett: 324 (1964)
8) Smith,
2867 (1949) 9) Timmermans,

Can. J. Chem. Eng.,

J. Chem. Eng. Data,
Ind. Eng. Chem., 41,
Constants

T.E. and R.F. Bonner:

J.: "The

Physico-Chemical

of Pure Organic Compounds," Elsevier Publishing Company, Inc., New York (1950)

CALCULATION OF MULTICOMPONENT DISTILLATION ACCOMPANIED BY A CHEMICAL REACTION'

ISAO SUZUKI, HIROSHI MITSUHO HIRATA YAGI, HIROMASA KOMATSU AND

Department of Industrial Chemistry, Faculty of Engineering, Tokyo Metropolitan University, Tokyo, Japan
Iterative method for the determination of stage temperatures, stage reaction rates and interstage flow rates in the problem of multicomponent distillation accompanied by a simultaneous chemical reaction is discussed, and the use of a modified Muller's method for the convergence of the column temperature profile is proposed. Derivation of the equation is simplified by using matrix notation, which also has the advantage that any interstage flow pattern is allowed. For the solution of the linearized material balance equation, the tridiagonal matrix algorithm is employed. Some problems are discussed to demonstrate the feasibility of the calculations and the fact that quadratic convergence is obtained.

occur during the rectification, is used in the ous production of esters. The theoretical its design problems has been proposed by and coworkers3-7). Marek8) and Belck2). But

The distillation

column reactor in which reactions

continubasis for Othmer as there

are considerable difficulties in solving a exact design problem, they used manual plate-to-plate calculations with very rough approximations in vaporliquid equilibrium and reaction rate relations. In the previous paper6), we described experimental

Received on December 22, 1969

26

results for the continuous production of ethyl acetate

26 ) JOURNAL OF CHEMICAL ENGINEERING OF JAPAN

in a distillation column reactor with sieve tray, and successive plate-to-plate design calculations with graphical techniques and empirical correlations. Furthermore, numerical correlations and a method of prediction for the vapor-liquid equilibrium accompanied by esterification have been also reported^).

The purpose of this paper is to present a method for the rigorous solution of problems in multicomponent distillation accompanied by a simultanous chemical reaction. When the reaction occurs on

each stage in a column, the material balance for each component and the heat balance on each stage will give a set of algebraic equations which may be expressed in a matrix if the effect of chemical reaction
in the basic relations is included. This method

employs the tridiagonal

developed by Amundson et al. for the solution of linearized material equations, and uses modified Muller's method for convergence of the column temperature profile. For agreement between the assumed and the calculated conversion of reaction, no method obtains more stable and rapid convergence than does the iterative method. To be specific, rectification accompanied with continuous production of ethyl acetate with equilib-

matrix algorithm, which was

rium established on each stage is used as illustration.

It is specified that the number of stages, feed plate location, condition of feed, reflux rate and overhead vapor drawoff were fixed in advance so that the composition profile through the column and conversion of reaction might be computed. 1. Method of Computation
Fig. 1 A model for the distillation column reactor

For the convenience of derivingsystem the general working equations, a hypothetical as shown in
Fig.1 is considered as a model column. This

column has n equilibrium stages including a condenser (partial, total or compound condenser) and a reboiler. The stages are numbered from top to bottom with the condenser as the first stage and the
reboiler as the n-th stage. It is assumed that one

feed stream Fj, one vapor side stream Gj, one liquid side stream Uj and one intercooler or interheater

Qj exist at each stage except for the condenser and the reboiler. Thus for a conventional column all the quantities of the external streams except Ff, QD,

Fig.

An ideal

equilibrium

stage

QB, D and W are zero. Each stage in the model column is assumed to be an equilibrium stage, that is, the vapor stream leaving the stage is in equilibrium with the liquid stream
leaving the same stage and the reaction rate is constant because of the steady state. Fig. 2 shows such an ideal equilibrium stage. There are generally four sets of equations which must be satisfied in a calculation for the rigorous equilibrium stage accompanied by a chemical reaction. They are the material balance equation, the vapor-liquid relation, the rate equation of reaction and the heat balance equation. For the case of a
VOL. 4 NO. 197I

chemical reaction in the fractionated mixture, the material and enthalpy balances must include terms expressing the influence of the reaction. Depending on what variables are chosen and how the material and heat balances are written, there are different ways to express the above equations. In this paper, the material and heat balances are written around each stage and the independent

variables are the mole fractions in liquid xij9 the vapor flow rate Vj, the reaction rate JRj and the temperature Tj. Referring to Figs, 1 and 2, the equations for the

model column are readily derived as follows:

:27;
27

The material balance around each stage

Lj^xtj^ - (Vj + Gj)yij - (Lj + Uj)xtJ+Vj+1yiJ+1 +i^+ ARj - 0 (1)

Aj=Lj^=Vj+

X]V*-Gk-Uk)-D 2^j^n-l 3 2(Fk-Ck-Uk)

k-2

where the sign ofreactants of products is plus. Vapor-liquid equilibrium total pressure, temperature

in ARj is minus and one ratio K^ depends and composition. on

B}= -Wi+GJKt,+F,+1+
-D+Uj] Cj=Vj+1Kij+1 Dj= -FjZijARj An=Vn+Gn+W-Fn

yiS -KijXtj = 0 Summations of vapor and liquid on each stage

i-1

(2) mole fractions

(3a)

2<j<n-1 2^j^n-l 2^j^n

(9)

Bn = -(Vn + Gn)Kin-W Dn = -FnZin ARn

the

(10)

Sva-1.o=o
2xtJ-1.o=o

or
1=1

Thisfollowing set of equations may be formally written as matrix equation.

AX=D (ll)

(3b)

The overall

reaction

rate

to be calculated

by over-

all material balance is equal to the summation of the

reaction rate on each stage, the reaction rate equation.
2JRj-AR=0 Heat balance equation around each stage
(4)

equilibrium

With the above manipulation of the material and

equations and further manipulation of

which

is calculated

by

summation of heat balance equation, these equations

at constant
i=l

pressure in a complex column become,

l^j^n

(3c)

m 2#*i&<j-1.0=0
(Hj+i ~ hj)Vj+1 +Fj(HFj-hj)-Qj When the flow - (Hj - hj) +JRjHrj rates

(12)

Lj^hj^ - (Vj + Gj)Hj - (Lj + Uj)hj + Vj+1Hj+1 +F,/^, - i + JRjHrj = 0

(Vj + GJ-ihj-hj-JLj-! = 0 l<j<n (13) and compositions of feed

for a given holdup,

The value of the reaction term may be calculated

composition, molal

volume and

temperature of the liquid if we know the dependence

streams are given, and the amounts of all the product streams are specified, Fjy set zip ofVj, Gj, Uj} D and Ware all constants. If an initial Tj and JR3 is

of the rate constant on the temperature and concentration of non-reacting components. For the case of production of ethyl acetate, the reaction term is as follows6)
AR, = krfj
X\j

assumed, Aj, Bj, Cj and Ds in Eq.(7) are also constant, provided that the equilibrium ratios

KiS can

be expressed as functions of Tj- Then the material

106

(5)

2 Pij%i
Considering that the esterification is an equimolal reaction, Eqs. (1) and (2) are combined and the liquid rate is expressed as functions of the vapor rate by an overall material balance.

balance equation (7) is a linear system. The solution of Eq.(7) for x{,j can be readily obtained by use of a simple algorithm derived from the
Gauss elimination method. Using this algorithm, values of x.Lj are calculated by first evaluating xin and receding backward with j decreasing until xn is reached. These equations are shown as follows; xij= Qj-Pj%ij+i Vi=CJB, qi = DJB, Vj - CjKBj-AjVj-x) qj = (Dj-Ajqj-JKBj When the xti obtained l<j<n-l (14)

L,=VJ+l+
where

2(Fk-Gk-Uk)-D
D=V1+U1

(6)

Then, the material balance to a tridiagonal matrix form.

equation

is reduced

2<j<n-1 -AjVj-i) 2^j^n-l from the above algorithm

ft%\

A2

B2 A,

C2 Bj Cj

Dj

is substituted into the reaction rate Eq.(12) and Kij can be expressed as a function of Tj, Eq.(12) becomes a function of Tj only and Muller's method is em(7)

A.n-i

>n-l An

(~"n-l Bn

ftin-1 ftin

A.-. A.

1<i<m

where=-VxKn-U-U,
C,

ployed for the solution of this equation. Muller's method is used in a modified form in this paper. When a quadratic curve is drawn through three points of temperature, and the root of this equation is taken as the approximation, one point is taken such that a value of the object function

= VoKi2

(8)
28'

+ JRi (reactant is plus and product is minus)

28

calculated from one point is contrary in sign to the values from other points. The real root can be always obtained by the above procedure. Then, this method
can provide the desired solution at the stable state.
JOURNAL OF CHEMICAL ENGINEERING OF JAPAN

Fig.

Block

diagram

of the

Muller's

method

Fig.

Block

diagram

Fig. 3 shows the calculation

method.

procedure of Muller's
3. Numerical Examples

equation, equation

WhenXij is obtained from the material balance

ARj is calculated from the reaction rate and Tj is obtained from the summation

equation by Muller's method, new values of Vj can

be calculated directly from the heat balance equation if enthalpies of feed streams and heat duties of the intercoolers or interheaters are given. 2. Computational Procedure procedure may be written as

Computational follows ;
perature Calculate

step by step calculations of the distillation column reactor are performed in three situations; the first is the case in which vapor-liquid equilibrium ratio Kij is a function of temperature only, the second is the case in which the activity coefficient is used to calculate the vapor-liquid equilibrium and the third is for the multifeed column. These methods have been programmed for IBM

As illustrative

examples for the proposed method,

360 digital computer, and The manyconvergence test problems have been successfully solved. criteria
used for these problems 2AT) = 2((Tj)twere; (T,),-i)2^0.Oln (15)

Step 1 Assume an initial vapor rate profile by means of constant molal overflow and linear temStep 2 and reaction rate profile. K.Lj and then calculate the ele-

ments of the matrix Aj, Bj, Cj and Dj. Step 3 Solve the material balance equation for x,Lj
Step Step 4 5 by using the tridiagonal matrix algorithm. Normalize the compositions of liquid. Substitute the calculated values of xtj and

The column is operated at ordinary pressure. There

A conventional reacting fractionator is considered.

and ARj is calculated for a new set. Calculate the enthalpies of the internal vapor and liquid streams. Step 7 Solve the heat balance equation for a new set of Vj. Step 8 Repeat steps (2) through (7) until the desired accuracy is obtained. Step 6

assumed values ofTj into the rate equation,

are 13 trays, including the reboiler and a total condenser. As the basis for the calculation a feed of 0.1076 moles per minute is used. The vapor overhead is 0.0208 moles per minute and the bottom

0.0868 moles per minute. The feed is preheated to

boiling point of the liquid. The reflux ratio is assumed to be 10. The feed stock is fed to the sixth stage from the top, and has the following composition; Acetic acid zx = 0.4962 Ethanol z2 = 0.4808 Water z3 = 0.0229 Ethyl acetate z4 = 0.0
'29'

The block diagram of such a computational tine is shown in Fig. 4.

VOL. 4 NO. 1 1971

rou-

29

component are approximated as a quadratic function of the temperature from the presented1-5>9) heat capacity and latent heat data. The vaporliquid equilibrium ratio fitted roughly as a function of temperature and the activity coefficient are shown in Table 1. The reaction rate equation is used as follows,
Table 1 Vapor-liquid equilibrium and enthalpy data

The enthalpies

of vapor and liquid for each pure

logfc=
a function

_A^xi01

+3.70
The holdup is taken as

where molal volume p^ in Eq.(5) is expressed4) as

of temperature.

1. Vapor-liquid Kx=2.25
LogK2= LogK3= LogKt=

equilibrium x 10~2/-2.3 -2.3 -2.3

ratio; 1.666

Ki

for the reboiler. As a first example, the case where the vapor-liquid equilibrium depends on temperature is considered. Starting with a linear temperature profile, a vapor rate profile corresponding to a constant molal overflow, and a conversion of reaction are assumed by rough calculation. Temperature throughout the

1.0 (/) at the bottom and 0.3 (/) at each stage except

x \03/T+6.58825 x 103/T+6.48351 x 103/T+6.74151

2. Activity coefficient Activity coefficients for this system are reported in the previous paper.10)
3. Enthalpy Vapor
2421.29 + 2.0142T + 2.80325 X 10-2T2-0.11363 x 10-4T3 -f 0.002005 x 10~6T4 H2 = - 3003.24+ 4.750T + 2.503 x 10"2T2 -0.8263 x 10~5r3+ 1.1975 x 10~3T4 H3 = 40.83193(T/100) + 0.36710(T2/100) + 0.0616 x 10-4T3 + 34.42355(100/T)
H4= 4981.59+ - 5.390

was set initially at 92C. Their temperatures were obtained by making a rough estimate of top and bottom compositions. The conversion of reaction

column must be assumed. For the problem at hand a temperature at the vapor outlet of the total condenser of 72C was taken, while the bottom temperature

based on ethanol is assumed to be 0.3. Table2

gives the computational results of this example.
is observed that Tj9 Vj, Lj, xi3- and JRj change slightly after second iteration. Temperature reaction rate used in the successive iterations
given in Fig. 5.

Hx = -

It

only and are

Hs; Btu/lb, 10.31T

x 10~6T3

T; R + 30.495

x 10"3T2

Next, to test the program for the case in which the vapor-liquid equilibrium is expressed by the

Liquid Liquid enthalpies can be calculated from the

latent heat and above vapor enthalpies.

Table 2 Final results

activity coefficient, the same problem is considered. In this case, the values of %,Lj require to calculate the activity coefficient. Then, the procedure is made to switch after five iterations by the vapor liquid
of the first example

Iteration
No.
1 2 3 4 5 6 7 8 9 10 ll 12 13 j

Temp.

number 7
-0.048 -0.044 -0.040 -0.042 -0.045 0.016 -0.002 -0.023 -0.042 -0.058 -0.078 -0.136 -0.198

Delta

where, No. ;; Stage number, kk; Trial number ofMuller's method Sum %i Composition profile xi:j AcOH EtOH Water AcOEt
0.0 0.22880 0.22612 0.22405 0.22229 0.22128 0.21898 0.21901 0.2 1892 0.21872 0.212846 0.21891 0.22465 0.20800 0.20532 0.20325 0.20149 0.20048 0.30578 0.30581 0.30572 0.30552 0.30526 0.30571 0.31145 0.08680
0.00000 0.00000 0.00001 0.00083 0.02524 0. 18996 0. 18908 0. 18850 0. 18849 0. 19056 0.20341 0.26740 0.47028 0.62822 0.7007 0.7552 0.79283 0.79752 0.67402 0.66120 0.64632 0.62735 0.60082 0.55776 0.47083 0.30064 1 1 0.01282 0.01820 0.02452 0.03 180 0.03920 0.04029 0.04944 0.06213 0.07999 0. 10509 0.13860 0. 17254 0.17014
0.34498 0.27037 0.21196 0. 16809 0.13309 0.09270 0.09766 0.10106 0.10288 0.10287 0.09984 0.08913 0.06216
3 4 1

72.781 73.461 74.023 74.482 75.370 79.399 79.371 79.387 79.466 79.656 80.184 82.025 87.647 Reac.mol
0.00000 0.00000 0.00000 0.00000 0.00000 0.00027 0.00027 0.00027 0.00028 0.00029 0.00036 0.00073 0.01014

0.98601 0.98928 0.99170 0.99355 0.99506 0.99696 0.99739 0.99801 0.99870 0.99933 0.99962 0.99990

1.00322

Composition profile
0.54656 0.62322 0.69404 0.74342 0.77743 0.78162 0.76584 0.74913 0.72959 0.70441 0.66875 0.61013 0.49150 0.00876 0.01282 0.01770 0.02343 0.03003 0.03671 0.04499 0.05658 0.07309 0.09680 0.13057 0.17568

Vi ,"

Sum :
0.98248 0.98601 0.98898 0.99117 0.99285 0.9942 1 0.99448 0.99507 0.99594 0.99691 0.99779 0.99819 0.99862

0.21855

Total
30

mole of reaction

= 0.01261

Conversion

= 0.24371
30)

Sum Delta 7\ = 0.07950

JOURNAL OF CHEMICAL ENGINEERING OF JAPAN

equilibrium in temperature. A converged solution was obtained in eight iterations after the switching.

Table 3 together with Fig. 6 shows the temperature, vapor rate and other profiles, which are in agreement with experimental of Run 7 in the previous paper6).
In this case, it is observed that Tj and other values change slightly after the switching. For the third example, a complex fractionator with two feeds, in which acetic acid is fed to the sixth stage from the top and ethanol to the second

The same constants and conditions as in the second example, except for the above feed, are used. The calculation is carried through ten iterations after five and the result of final iterations is shown in Table 4. 4. Evaluation of Method be solved very stable algorithm. 6 method,

stage from the bottom, is considered. The feed rate

of acetic acid and ethanol is 0.0538 mole per minute.

The material balance equation could simultaneously for each component at state by using the tridiagonal matrix When the same problem was solved by

Fig. 5 Temperature first example

and reaction

rate

profiles

for the

Fig. 6 Composition second example

and temperature

profiles

for

the

Table

Final

results

of the

second

example
AcOEt
0.48928 0.44900 0.39478 0.32565 0.24087 0.14565 0.13404 0.12117 0.10758 0.09373 0.07984 0.06587 0.05103

Iteration number13 No.j Temp. Delta Composition profileWater %y Tj Tj Vj Lj AcOH EtOH

~1 72.769 0.010 0.011 0.011 0.006 -0.014 -0.007 -0.026 -0.024 -0.041 -0.042 -0.042 -0.056 -0.058 O0 0.22880 0.22736 0.22536 0.22262 0.21948 0.21695 0.21618 0.21534 0.21446 0.21366 0.21379 0.21971 0.20800 0.20656 0.20456 0.20182 0.19868 0.30375 0.30298 0.30214 0.30126 0.30045 0.30059 0.30651 0.08680 0.00000 0.00000 0.00006 0.00144 0.02749 0.19287 0.19266 0.19259 0.19297 0.19568 0.21062 0.27586 0.44682 0.45017 0.49419 0.54799 0.61101 0.66266 0.59829 0.59742 0.59480 0.58870 0.57551 0.54484 0.46810 0.31985 0.05735 0.05412 0.05522 0.06074 0.06846 0.06321 0.07616 0.09181 0.11107 0.13522 0.16459 0.18999 0-18293 2 72.932 3 73.156 4 73547 5 74.698 6 80.103 7 80.337 8 80.609 9 80.923 10 81.335 l 82196 12 84.962 13 92.139

Sum %i
0.99680 0.99732 0.99806 0.99885 0.99948 1.00002 1.00027 1.00037 1.00031 1.00012 0.99989 0.99982 1.00063

kk
F~~ 4 5 3 1 1 3 4 4 4 1 1 1

j Reac. mol
1 2 3 4 5 6 7 8 o00000 0.00000 0.00000 000000 000000 0.00027 0.00029

Composition profile
0.00000 0.00000 0.00000 0.00005 0.00131 0.02491 0.02521 0.02563 0.64389 0.02627 0.02761 0.03246 0.05571 0.15521 0.41687 0.45017 0.49016 0.53896 0.59598 0.64254 0.64363 0.09826 0.64179 0.63490 0.61818 0.57718 0.47356

yij
0.06434 0.05735 0.05442 0.05542 0.06043 0.06739 0.08137 0.11892 0.14460 0.17702 0.21616 0.24589 0.51520 0.48928 0.45268 0.40351 0.34094 0.26440 0.24957 0.23234 0.21328 0.19307 0.17226 0.15054 0.12484

Sum yi
0.99641 0.99680 0.99727 0.99794 0.99866 0.99923 0.99977 1.00012 1.00026 1.00018 0.99992 0.99959 0.99950

0.00030 9 0.00032 10 0.00035 l 000045 12 0.00094 13 0.01166

Totalmol.
VOL.4 NO.

of reaction
1 1971

= 0.01460

Conversion
(31)

= 0.28215

SumDelta

T5 = 0.01363

___
31

No.

Temp.

Delta
-0.005 0.001 -0.001 -0.002 0.019 0.062 0.141 0.183 0.179 0.138 0.091 0.067 0.058

Iteration
Vj

Table 4 Final results of the third number 15 Composition profile

Lj AcOH EtOH
0.00000 0.00000 0.00007 0.00178 0.03704 0.23940 0.24165 0.2443 0.24665 0.24900 0.25474 0.24777 0.44803

example Xi j
0.14851 0.13088 0.11710 0.10766 0.10310 0.09223 0.10540 0.11986 0.13307 0.14237 0.14560 0.13993 0.13620

Water

AcOEt

Sumxt
3 1

1 72.002 2 72.071 3 72.155 4 72.286 5 73.154 6 79.408 7 80.069 8 80.983 9 82.013 10 82.974 1 1 83.854 12 85.032 13 92.014 j Reac. mol

0.0 0.20800 0.22880 0.20810 0.22890 0.20791 0.22871 0.20713 0.22793 0.20528 0.22608 0.25545 0.22245 0.25294 0.2 1994 0.25048 0.2 1 748 0.24842 0.2 1542 0.24700 0.2 1400 0.24642 0.21342 0.30635 0.2 1955 0.08680

0.31310 0.33352 0.35589 0.38079 0.40048 0.35337 0.39576 0.43963 0.47901 0.50983 0.53008 0.53433

0.37299

0.53551 0.53243 0.52355 0.50603 0.45512 0.30991 0.25186 0.19215 0.13914 0.09843 0.07044 0.05216 0.04346

Composition profile
0.00000 0.00000 0.00000 0.00006 0.00162 0.03365 0.03465 0.03670 0.03957 0.04281 0.04703 0.05640 0.15633 = 0.27837

y-i j

Sum ;
0.99723 0.99712 0.99686 0.99665 0.99633 0.99586 0.99388 0.99360 0.99506 0.99727 0.99931 1.00072 1.00138

1 2 3 4 5 6 7 8 9 10 ll 12 13

0.00000 0.00000 0.00000 0.00000 0.00001 0.00035 0.00040 0100047 0.00055 0.00062 0.00071 0.00089 0.01099

0.29571 0.31310 0.33166 0.35200 0.37461 0.39246 0.43666 0.48816 0.54185 0.59073 0.62992 0.65692 0.54817

0.16708 0.14851 0.13248 0.11996 0.11138 0.10725 0.11821 0.13185 0. 14668 0.15968 0.16772 0.16824 0.19134

0.53443 0.53551 0.53271 0.52464 0.50872 0.46249 0.40437 0.33688 0.26696 0.20405 0.15463 0.11917

0.10554

Total mol. of reaction

= 0.01498

Conversion

Sum Delta

Tj = 0.12477

but no negative values of x.hj were found in this method. Muller's method for convergence may be good for this typical calculation as compared with the Newton-Raphson method, for the reason that when the first example was solved by the Newton-Raphson method, there were a few cases which do not converge in the iteration, while Muller's method gave a con-

negative values of the mole fraction x^ were obtained,

Nomenclature
D

overhead distillate product feed rate at the feed plate

rate

HF

verged solution.
5. Conclusions A detailed and completely automatic method of determining the multicomponent separation accompanied by a chemical reaction achieved by a fractionating column reactor with fixed conditions

Ti=
J

feed rate at stage j vapor side stream from stage j enthalpy of the liquid stream Lj enthalpy of the vapor stream Vj enthalpy of the feed stream Fj
component number stage number

reaction
liquid
n m

iteration numberor dummy subscript holdup at stage j

rate constant at stage j
stream flowing

[mole/min] [mole/min] [mole/min] [mole/min] [cal/mole] [cal/mole] [cal/mole] [-] [-] [-]
[//mole-min]

equilibrium ratio of component i at stage j

down from stage j to stage

has been derived and demonstrated of by means of the tridiagonal method for solution the material
balance equation and Muller's method for con-

pi Qb
Qd

vergence of temperature. Oncethe operating parameters are prescribed and the initial distribution of temperature, vapor rate and reaction rate is estimated, no manual intervention is required to obtain the solution. The method converges rapidly and stably.
Acknowledgement We are very grateful
able
32

Us V,-

(.7 + 1) [mole/min] total number of components of mixture [-] total numberof stages in the complex column[-] [mmHg] vapor pressure of component i [cal/min] heat duty of the reboiler [cal/min] heat duty of the condenser [mole/min] reaction rate at stage j [C] temperature at stage j [mole/min] liquid side stream from stage j vapor stream leaving stage j to stage (j -\- 1)
[mole/min]

W= bottom product

[mole/min] Xij = composition of the liquid stream leaving stage j [mole fr.]
Vij = composition of the vapor stream leaving stage j

to the

Chiyoda

Chem. Eng.

and Const. Co., Ltd. for making the computer availfor this study.
32'

[mole fr.] Zij = composition of the feed stream entering stage j [mole fr.] pij = molar volumeof component/ at stage j
JOURNAL OF CHEMICAL ENGINEERING

[m//mole]

OF JAPAN

Literature

cited

6) Komatsu, H., I. Suzuki, T. Ishikawa and M. Hirata: Kagaku Kogaku, 34,D.F. 45 (1970) 7) Leyes, C.E., Othmer: Trans. Am. Inst. Chem.
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REMOVAL OF A SMALL AMOUNT OF WATER IN ACETONE BY AZEOTROPIC DISTILLATION EMPLOYING ETHYLBROMIDE AS SEPARATING AGENT
MASASHI UNO, AKIRA NAKAE**, JIRO SUDOH, YASUO HIROSE AND MITSUHO HIRATA

Chemical Engineering Laboratory, Tokyo Metropolitan University, Tokyo, Japan

The rapid growth of the petrochemical industry leads to a demand for highpurity acetone. However, removal of a small amount of water in acetone to less than 1400 ppm by ordinary distillation is a difficult problem. After investigation of removal of micro water in acetone, it has been found that azeotropic distillation employing ethylbromide as separating agent is effective. As basic data for the design of an azeotropic tower, the following physical properties have been measured. 1) Vapor-liquid equilibrium of the binary systems ethylbromide-water at 760 mm of Hg in the region of ethylbromide-rich side and ethylbromide-acetone at 760 mmof Hg. 2) Solubility of water in ethylbromide at 0, 10, 20, 30, 34.7C. Using ethylbromide as separating agent, azeotropic batch distillations have been carried

out through a packed tower. As a result,ithas can be reduced to less than 200 ppm.

been found thatmicro water in the feedstock

and ordinary
Introduction

distillation

can be used to remove a

small amountof water from an acetone stream.

The difficulty of comesuccessfully ing ethylbromide distillation was

of trouble in some subsequent processing step. Hydrate formation, decreased catalyst activity, or increased corrosion are examples of problems which have arisen in industry as a result of insufficient

The dehydration of acetone is necessary wherever the water held in solution mayprove to be a source

dehydration, however, was overby azeotropic distillation employas separating agent, after ordinary found unsatisfactory. Evaluation

of the performance of azeotropic distillation

removal of water by conventional distillation

Various processes such as absorption,

adsorption

alone.

* Received

* * Chemical

onJuly

Engineering

25, 1970

Laboratory,

Toa

Oil

Co.,

a knowledge of the vapor-liquid equilibrium for ethylbromide-water and ethylbrornide-acetone systems and the solubility of water in ethylbromide. The determination of these equilibrium and solubility values constitutes an important part of the design of an azeotropic distillation tower. Therefore, these equilibrium and solubility values were measured.

requires

Kawasaki, Japan
VOL. 4 NO. 1 1971

According to the results, it was found possible to re33)

33