Table 7 Extractive

distillation
with
bromide
RunNo.
FeedcomSaltcon-

position

zinc

position of

C [wt%]

Nomenclature

bottom product,

mole%
methylene chloride
0

4.65
4.65
4.65
4.65
3.20

3.20
3.20
3.20

agent, the methylene chloride content of acetone can

be reduced to 0.09 mole% or less.

1
2
6

12.00
5.35

containing
Vaporcom-

centration

mole%
methylene
chloride

10

reflux

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

C = salt (wt%) in methylene chloride-acetone-salt

liquid
phase
x1 = mole fraction ofmethylene chloride in liquid phase

(salt-free

Literature

cited

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

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)

Conclusions
Vapor-liquid
equilibrium
data
pressure of the system: methylene
with zinc bromide,
zinc chloride

basis)

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

at atmospheric
chloride-acetone
and potassium

5) Long, F.A. and W.F. McDevit:

Chem. Rev.,

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

Can. J. Chem. Eng.,

7) 9, Ramalho,
R. S. and N. S. Edgett:
324 (1964)

J. Chem. Eng. Data,

(1952)

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

8) Smith,

T.E. and R.F. Bonner:

2867 (1949)
9)
Timmermans,

J.:

"The

51, 119

Ind. Eng. Chem., 41,

Physico-Chemical

Constants

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.

The distillation

column reactor in which reactions

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

Received on December 22, 1969

26

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

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.

employs the tridiagonal

This

method

matrix algorithm, which was

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-

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

Fig.

of Computation

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

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.

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
4

NO.
197I

An ideal

equilibrium

stage

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

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

VOL.

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

Aj=Lj^=Vj+

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

where the sign ofreactants

of products
is plus.
Vapor-liquid
equilibrium
total pressure, temperature

2^j^n-l
3
2(Fk-Ck-Uk)

(1)

in ARj is minus and one

B}= -Wi+GJKt,+F,+1+

ratio K^ depends
and composition.

-D+Uj]
Cj=Vj+1Kij+1
Dj= -FjZijARj

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

on

(2)
mole fractions

Sva-1.o=o

k-2

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

(9)

An=Vn+Gn+W-Fn

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

(3a)

i-1

(10)

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

the

or
2xtJ-1.o=o

The overall

reaction

rate

AX=D

(3b)

1=1

to be calculated

reaction rate on each stage,

the reaction rate equation.

which

is calculated

equilibrium

Heat

balance

equation

at constant

each

composition,

molal

(4)

When the

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

106

stant,

is reduced

C2

A,

Bj

A.n-i

B2

Cj

>n-l
An

Dj

(~"n-l
Bn

ftin-1

A.-.

ftin

A.

where=-VxKn-U-U,

= VoKi2

the

equilibrium

ratios

KiS can

l<j<n-l

(14)

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

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

(7)

1<i<m

C,

that

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-

ft%\

A2

provided

xij=
Qj-Pj%ij+i
Vi=CJB,
qi = DJB,
Vj - CjKBj-AjVj-x)
qj = (Dj-Ajqj-JKBj
When the xti obtained

(6)

equation

rates

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;

D=V1+U1

Then, the material

balance
to a tridiagonal
matrix form.

flow

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

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

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.

where

- (Hj - hj)
+JRjHrj

be expressed as functions of Tj- Then the material

(5)

2(Fk-Gk-Uk)-D

(12)

assumed, Aj, Bj, Cj and Ds in Eq.(7) are also con-

2 Pij%i

L,=VJ+l+

l^j^n

streams are given, and the amounts of all the product

streams
are specified,
Fjy setzip ofVj,
Gj, Uj}Tj Dandand JR3
Wareis
all constants.
If an initial

volume and

temperature of the liquid if we know the dependence

X\j

of

pressure in a complex column become,

(Hj+i ~ hj)Vj+1
+Fj(HFj-hj)-Qj

The value of the reaction term may be calculated

for a given holdup,

manipulation

i=l

stage

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

and further

m
2#*i&<j-1.0=0

(3c)
around

equations

summation of heat balance equation, these equations

by

2JRj-AR=0

(ll)

With the above manipulation of the material and

by over-

all material balance is equal to the summation of the

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

(8)

can provide

+ JRi (reactant is plus and product is minus)

28

X]V*-Gk-Uk)-D

28'

the desired

solution

at the stable

JOURNAL OF CHEMICAL ENGINEERING

state.

OF JAPAN

Fig.

Block

diagram

of the

Fig. 3 shows the calculation

method.

Muller's

method

Fig.

3.

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

Procedure

Computational
follows ;

procedure

may be

written

as

perature
Calculate

and reaction rate profile.

K.Lj and then calculate

the

4
5

2AT)

ele-

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

NO.

1971

(15)

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

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.

VOL.

(T,),-i)2^0.Oln

A conventional reacting fractionator is considered.

by using the tridiagonal

matrix algorithm.
Normalize the compositions
of liquid.
Substitute
the calculated
values of xtj and

The block diagram of such a computational

tine is shown in Fig. 4.

= 2((Tj)t-

were;

The column is operated at ordinary pressure. There

assumed values ofTj into the rate equation,

Step

examples for the proposed method,

used for these problems

ments of the matrix Aj, Bj, Cj and Dj.

Step 3 Solve the material balance equation for x,Lj
Step
Step

Examples

360
digital computer,
and The
manyconvergence
test problemscriteria
have
been successfully
solved.

Step 1 Assume an initial vapor rate profile by means

of constant molal overflow and linear temStep

Numerical

As illustrative

be calculated
directly
from the heat balance equation if enthalpies
of feed streams and heat duties of
the intercoolers
or interheaters
are given.
Computational

diagram

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

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

2.

Block

procedure of Muller's

WhenXij is obtained from the material balance

equation,
equation

rou'29'

29

The enthalpies

of vapor and liquid for each pure

logfc=

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,
Vapor-liquid

equilibrium

and

equilibrium
x 10~2/-

LogK2=
LogK3=
LogKt=

-2.3
-2.3
-2.3

enthalpy

ratio;
1.666

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

a function

data

Ki

was set initially

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

based on ethanol is assumed to be 0.3. Table2

gives the computational

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)

Hs; Btu/lb,
10.31T

T;+ 30.495
R

given

x 10"3T2

can be calculated

from the

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

30

mole of reaction

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

Composition profile

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

Total

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

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

= 0.01261

Conversion

= 0.24371
30)

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

Vi ,"

0.21855

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

0.0
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

where, No. ;; Stage number, kk; Trial number ofMuller's method

Sum %i
Composition profile xi:j
AcOH EtOH
Water AcOEt

Reac.mol

example

-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

first

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

of the

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

Delta

results

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

number 7

Temp.

Final

5.

Iteration

Fig.

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

latent heat and above vapor enthalpies.

Table

in

It

only
and
are

Next, to test the program for the case in which

the vapor-liquid
equilibrium
is expressed
by the

x 10~6T3

enthalpies

example.

Liquid

of this

4981.59+
- 5.390

results

is observed
that Tj9 Vj, Lj, xi3- and JRj change
slightly
after
second iteration.
Temperature
reaction rate used in the successive
iterations

Liquid

No.

as

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

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

Hx = -

is taken

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

Enthalpy
Vapor

H4=

The holdup

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

2. Activity coefficient
Activity coefficients for this system are reported
in the previous paper.10)
3.

of temperature.

+3.70

Table

1. Vapor-liquid
Kx=2.25

_A^xi01

1.00322

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

Sum Delta 7\ = 0.07950

JOURNAL OF CHEMICAL ENGINEERING

OF JAPAN

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.

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

4.

of acetic acid and ethanol is 0.0538 mole per minute.

and reaction

rate

profiles

Table

Fig. 6 Composition
second example

for the

Final

of Method

The material balance equation could

simultaneously
for each component at
state by using the tridiagonal
matrix
When the same problem was solved by

stage from the bottom, is considered. The feed rate

Fig. 5 Temperature
first example

Evaluation

results

of the

second

and temperature

72.769

0.010

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

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

j Reac. mol
1
2
3
4
5
6
7
8

0.00030
9
0.00032
10
0.00035
l
000045
12
0.00094
13
0.01166

Totalmol.
VOL.4

0.00000

0.45017

0.05735

0.48928

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
0.00006
0.00144
0.02749
0.19287
0.19266
0.19259
0.19297
0.19568
0.21062
0.27586
0.44682

0.49419
0.54799
0.61101
0.66266
0.59829
0.59742
0.59480
0.58870
0.57551
0.54484
0.46810
0.31985

0.05412
0.05522
0.06074
0.06846
0.06321
0.07616
0.09181
0.11107
0.13522
0.16459
0.18999
0-18293

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

Composition profile

NO.

0.02563

of reaction
1

1971

AcOEt

0.20800

o00000
0.00000
0.00000
000000
000000
0.00027
0.00029

= 0.01460

0.00000
0.00000
0.00000
0.00005
0.00131
0.02491
0.02521

0.41687
0.45017
0.49016
0.53896
0.59598
0.64254
0.64363

0.64389
0.02627
0.02761
0.03246
0.05571
0.15521

0.64179
0.63490
0.61818
0.57718
0.47356

Conversion
(31)

for

the

example

Iteration number13
No.j Temp.
Delta
Composition
profileWater %y
Tj
Tj
Vj
Lj
AcOH
EtOH
~1

profiles

be solved
very stable
algorithm.
6 method,

yij

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

Sum yi

0.06434
0.05735
0.05442
0.05542
0.06043
0.06739
0.08137

0.51520
0.48928
0.45268
0.40351
0.34094
0.26440
0.24957

0.99641
0.99680
0.99727
0.99794
0.99866
0.99923
0.99977

0.11892
0.14460
0.17702
0.21616
0.24589

0.23234
0.21328
0.19307
0.17226
0.15054
0.12484

1.00012
1.00026
1.00018
0.99992
0.99959
0.99950

0.09826

= 0.28215

Sum %i

SumDelta

T5 = 0.01363

___
31

No.

Temp.

Iteration

Delta

Lj

AcOH

example

EtOH

Xi j

AcOEt

Water

Sumxt

Reac.

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

mol

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

Composition profile

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

Total mol. of reaction

= 0.01498

Conversion

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

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

Sum Delta

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

3
3
1
1
1

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

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

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

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

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

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

Vj

Table 4 Final results of the third

number 15
Composition profile

y-i j

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

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

0.10554

Tj = 0.12477

negative values of the mole fraction x^ were obtained,

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-

Nomenclature
overhead distillate
product
feed rate at the feed plate

HF

Ti=

verged solution.
Conclusions

5.

m
n

balance

Qd

Muller's

method

for

iteration numberor dummysubscript

holdup at stage j
liquid

piQb

and

component number
stage number

rate constant

at stage j

[//mole-min]

equilibrium ratio of component i at stage j

has
been derived
and demonstrated ofby means
of the
tridiagonal
method for solution
the material
equation

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

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

reaction

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

rate

con-

vergence of temperature. Oncethe operating param-

stream

flowing

down from stage j to stage

(.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)

eters 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.

Us
V,-

Acknowledgement

Vij = composition of the vapor stream leaving stage j

We are very grateful

to the

Chiyoda

[mole/min]

W= bottom product

[mole/min]
Xij = composition of the liquid stream leaving stage j
[mole fr.]
[mole fr.]
Zij = composition of the feed stream entering stage j
[mole fr.]
pij = molar volumeof component/ at stage j

Chem. Eng.

and Const. Co., Ltd. for making the computer available

32

for this

study.

[m//mole]

32'

JOURNAL OF CHEMICAL ENGINEERING

OF JAPAN

Literature

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.

cited

1) Petroleum
"Technical Institute
Data Book-Petroleum
Refining", American
(1966)
2)

Belck,

L.H.:

A.LCh.E.

3) Berman, S., H. Isbenjian,

Ind.

4)

Eng. Chem.,

"International
(1926-1939)

40(ll),

Journal,

1,

467

Engrs., 41, 157 (1945)

Marek,
J.: Collection
Czechoslov.
Chem. Commun., 19,
621,
1055 (1954)
9)
Sato,
K.: "Bussei
Josu
Suisanhd",
Maruzen
(1954)
8)

(1955)

A. Sedoff and D. F. Othmer:

2139 (1948)

Critical

Tables",

10)Japan,
Suzuki,3(2), I.,

McGraw-Hill,

152

H. (1970)
Komatsu and M. Hirata:J.

Chem. Eng.

ll) 45(8),Wang, 155J. C.

and G. E. Henke: Hydrocarbon Processing,
(1966)

5) (1968)
"Kagaku Kogaku Binran" revised 3rd ed.5 Maruzen

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

The difficulty of
comesuccessfully
ing ethylbromide
distillation
was

The dehydration of acetone is necessary wherever

the water held in solution mayprove to be a source

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

removal of water by conventional distillation

processes

* Received

* * Chemical

such

onJuly

as absorption,

25, 1970

Engineering

Laboratory,

alone.

Oil

NO.

1971

requires

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.

adsorption

Toa

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

of the performance of azeotropic distillation

Co.,

According to the results, it was found possible to re-

Kawasaki, Japan
VOL.

can be used to remove a

small amountof water from an acetone stream.

Introduction

Various

distillation

33)

33