Extractive and Azeotropic Distillation PDF

Extractive and Azeotropic
Distillation
In Extractive and Azeotropic Distillation; Tassios, D.;

Advances in Chemistry; American Chemical Society: Washington, DC, 1974.

Extractive and Azeotropic

Distillation
Based on papers presented at

two symposia sponsored by the
Division of Industrial and
Engineering Chemistry
of the American Chemical Society
at the 160th Meeting, Chicago,
Ill., Sept. 17, 1970, and the
163rd Meeting, Boston, Mass.,
April 14, 1972.
Dimitrios P. Tassios
Symposia
Chairman
115
ADVANCES IN CHEMISTRY SERIES
AMERICAN CHEMICAL SOCIETY

WASHINGTON,
D.
C.
1972

ADCSAJ 115 1-176 (1972)
Copyright 1972
American Chemical Society
All Rights Reserved
Library of Congress Catalog Card 72-92811

ISBN 8412-0157-9
PRINTED IN THE UNITED STATES OF AMERICA

Advances in Chemistry Series

Robert F . G o u l d ,
Editor
Advisory Board
Bernard D. Blaustein
Paul N. Craig
Gunther Eichhorn
Ellis K . Fields
Fred W. McLafferty
Robert W. Parry
Aaron A. Rosen
Charles N. Satterfield
Jack Weiner

FOREWORD
A D V A N C E S
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C H E M I S T R Y
SERIES
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CONTENTS
PREFACE
DIMITRIOS P. TASSIOS
ix-xi
1 Dehydration of Aqueous Ethanol Mixtures by Extractive Distillation

C. BLACK and D. E. DITSLER
1-15
2 Process Design Considerations for Extractive Distillation: Separation of PropylenePropane

ROMESH KUMAR, JOHN M. PRAUSNITZ, and C. JUDSON KING
16-34
3 Extractive Distillation by Salt Effect
WILLIAM F. FURTER
35-45
4 Rapid Screening of Extractive Distillation Solvents: Predictive and Experimental

Techniques
46-63
5 Azeotropic Distillation Results from Automatic Computer Calculations
CLINE BLACK, R. A. GOLDING, and D. E. DITSLER
64-92
6 Prediction of Isobaric Vapor-Liquid Equilibrium Data for Mixtures of Water

and Simple Alcohols
A. ANDIAPPAN and A. Y. McLEAN
93-107
7 Demulsification of Crude Oils: Use of Azeotropic Distillation
LESLIE L. BALASSA and DONALD F. OTHMER
108-121
8 Distillation Calculations with Nonideal Mixtures

JOSEPH A. BRUNO, JOHN L. YANOSIK, and JOHN W. TIERNEY
122-135
9 Isobaric Vapor-Liquid Equilibrium in the Acetic Acid-Acetone System

R. JOE BURKHEAD and J. THOMAS SCHRODT
136-147
10 Separation of Water, Methyl Ethyl Ketone, and Tetrahydrofuran Mixtures

HUGH M. LYBARGER and HOWARD L. GREENE
148-158
11 Prediction of Vapor Composition in Isobaric Vapor-Liquid Systems Containing
Salts at Saturation
D. JAQUES and W. F. FURTER
159-168
INDEX
171-176
PREFACE
z e o t r o p i c a n d extractive d i s t i l l a t i o n s h a v e b e e n u s e d t h r o u g h the years
i n the c h e m i c a l i n d u s t r y to separate m i x t u r e s w h e r e the r e l a t i v e
v o l a t i l i t y o f the k e y c o m p o n e n t s is v e r y close, o r e q u a l , to u n i t y .
Appli-
cations f r o m the c l a s s i c a l d e h y d r a t i o n o f a l c o h o l w i t h b e n z e n e
(J)
m o r e recent ones s u c h as the p r o p y l e n e - p r o p a n e s e p a r a t i o n
(2)
to
and
aromatics recovery from hydrocarbon mixtures w i t h N-methylpyrrolidone

( 3 ) , i n d i c a t e a c o n t i n u o u s interest t h r o u g h the years i n this area.
T h e s e s e p a r a t i o n m o d e s h a v e n o t b e e n u s e d as f r e q u e n t l y as t h e y
s h o u l d i n i n d u s t r y , a n d the often u s e d reasons o f h i g h i n v e s t m e n t a n d
h i g h o p e r a t i n g costs are often w e a k w h e n one does a n i n - d e p t h s t u d y . T h e
r e a l reason lies w i t h t h e t i m e a n d m o n e y r e q u i r e d to o b t a i n a satisfactory
d e s i g n (4).
B e c a u s e o f the h i g h n o n i d e a l i t y o f the systems
involved,
solvent selection, d e s c r i p t i o n o f the n o n i d e a l i t y o f the phases, a n d trayto-tray c a l c u l a t i o n s are rather difficult. R e c e n t d e v e l o p m e n t s i n this area,
h o w e v e r , s h o u l d g r e a t l y f a c i l i t a t e this task, e s p e c i a l l y for e x t r a c t i v e d i s tillation.
S o l v e n t selection for a z e o t r o p i c d i s t i l l a t i o n is b a s e d o n r a t h e r
qualitative criteria discussed b y B e r g
( 5 ) , but
for e x t r a c t i v e
l a t i o n the q u a l i t a t i v e a p p r o a c h o f P r a u s n i t z a n d A n d e r s o n (6)
e m p i r i c a l correlations o f P i e r o t t i et ah (7),
distil-
a n d the
W e i m e r and Prausnitz
(8),
H e l p i n s t i l l a n d V a n W i n k l e ( 9 ) , a l o n g w i t h the t e c h n i q u e u s i n g g a s l i q u i d c h r o m a t o g r a p h y b y Tassios (10, 11)
give reliable, r a p i d methods
for solvent selection. F o r e x a m p l e , f o u r to five solvents c a n b e screened

i n one d a y b y u s i n g g a s - l i q u i d c h r o m a t o g r a p h y .
e x t r a c t i v e agents (12)
A l s o use o f salts as
provides a n e w dimension i n extractive distillation
separations.
T h e d e v e l o p m e n t o f e q u a t i o n s t h a t successfully p r e d i c t m u l t i c o m p o n e n t phase e q u i l i b r i u m d a t a f r o m b i n a r y d a t a w i t h r e m a r k a b l e a c c u r a c y for e n g i n e e r i n g purposes not o n l y i m p r o v e s the a c c u r a c y o f tray-tot r a y c a l c u l a t i o n s b u t also lessens the a m o u n t of e x p e r i m e n t a t i o n r e q u i r e d
to e s t a b l i s h the p h a s e e q u i l i b r i u m d a t a . S u c h equations are: the W i l s o n
e q u a t i o n ( 1 3 ) , the n o n - r a n d o m t w o - l i q u i d ( N R T L ) e q u a t i o n (14),
the l o c a l effective m o l e fractions ( L E M F )
parameter
v e r s i o n o f the
L a r s o n a n d Tassios (17)
e q u a t i o n (15,
b a s i c a l l y three-parameter
16),
and
a two-
NRTL
equation.
s h o w e d that the W i l s o n a n d N R T L
equations
p r e d i c t a c c u r a t e l y t e r n a r y a c t i v i t y coefficients f r o m b i n a r y d a t a ; H a n k i n s o n et al (18)
d e m o n s t r a t e d t h a t the W i l s o n e q u a t i o n p r e d i c t s a c c u r a t e l y
ix

m u l t i c o m p o n e n t v a p o r c o m p o s i t i o n s u p to five c o m p o n e n t s f r o m b i nary data.
T h e s a m e s t u d y i n d i c a t e s that w h e n l i m i t e d b i n a r y d a t a
a v a i l a b l e , t h e one p a r a m e t e r T a s s i o s - W i l s o n e q u a t i o n (19)
are
predicts m u l -
t i c o m p o n e n t u p to five c o m p o n e n t s d a t a w i t h g e n e r a l l y g o o d a c c u r a c y .
T h e W i l s o n e q u a t i o n c a n also b e u s e d successfully to c o r r e l a t e p h a s e
e q u i l i b r i u m d a t a i n the presence o f salts (20).
The N R T L and
LEMF
equations c a n also p r e d i c t successfully t e r n a r y l i q u i d - l i q u i d e q u i l i b r i u m

d a t a f r o m the b i n a r y d a t a w i t h the latter p r o v i d i n g b e t t e r results
(21).
R e g a r d i n g v a p o r p h a s e n o n i d e a l i t i e s , the e m p i r i c a l c o r r e l a t i o n o f O ' C o n n e l l a n d P r a u s n i t z (22)
p r o v i d e f u g a c i t y coefficients o f sufficient a c c u r a c y
for e n g i n e e r i n g purposes.
D e s i g n considerations o f a z e o t r o p i c d i s t i l l a t i o n
schemes are d i s c u s s e d b y R o b i n s o n a n d G i l l i l a n d ( 2 3 ) , H o f f m a n
a n d r e c e n t l y b y B l a c k et al.
(25),
w h o present a c o m p u t e r
(24),
oriented
approach.
F o r e x t r a c t i v e d i s t i l l a t i o n t h e presence o f the s e c o n d feed
(solvent)
presents s o m e c o m p u t a t i o n a l c o m p l i c a t i o n s i n m a i n t a i n i n g s t a b l e c o n v e r g e n c e i n the s o l u t i o n b y c o m p u t e r s o f the a p p r o p r i a t e system o f e q u a tionsi.e., m a t e r i a l a n d e n t h a l p y balances a n d e q u i l i b r i u m r e l a t i o n s h i p .

T h e a l g o r i t h m s t h a t c a n i n h e r e n t l y c o p e w i t h m u l t i p l e feeds are m a t r i x
o r i e n t e d , a n d the N e w t o n - R a m p h s o n p r o c e d u r e o f s o l v i n g these e q u a tions shows the m a x i m u m d e g r e e o f s t a b i l i t y (4).
S e v e r a l p a p e r s discuss
computational approaches for extractive distillation calculations ( A m u d s o n a n d P o n t i n e n (26),
N a p h t h a l i (27),
R o c h e (4),
B r u n o et al.
(28),
Black and Ditsler ( 2 9 ) , a n d others).

I n c o n c l u s i o n , r e c e n t d e v e l o p m e n t s i n solvent selection, p h a s e n o n i d e a l i t y d e s c r i p t i o n , a n d tray-to-tray c a l c u l a t i o n schemes
have
f a c i l i t a t e d the d e s i g n o f e x t r a c t i v e a n d a z e o t r o p i c d i s t i l l a t i o n
greatly
schemes,
a n d use o f salts g i v e n e w m e t h o d s f o r extractive d i s t i l l a t i o n separations.

F i n a l l y , the w o r k o f G e r s t e r ( 3 0 ) , B l a c k a n d D i t s l e r ( 2 9 ) , a n d B l a c k
et al. (25)
c o m p a r e these t w o schemes.
Newark College of Engineering

Newark, N . J. 07102
July, 1972
Literature Cited
1. Guinot, H., Clark, F. W., Trans. Inst. Chem. Engr. (London) (1938) 16,
187.
2. Hasflund, E. R., Chem. Eng. Progr. (1969) 65, 9.
3. Mueller, E., Hoehfeld, G., WorldPetrol.Congr., 8th, Moscow (June 1971).
4. Roche, Ed., 160th Natl. Meet. Amer. Chem. Soc., Chicago, 1970.
5. Berg, L., Chem. Eng. Progr. (1969) 65, 9, 52.
x

6. Prausnitz, J. M., Anderson, R., A.I.Ch.E. J. (1961) 7, 96.

7. Pierotti, G. I., Deal, C. H., Derr, E. L., Ind. Eng. Chem. (1955) 51, 95.
8. Weimer, R. F., Prausnitz, J., Petrol. Refiner (1965) 44, 9, 237.
9. Helpinstill, J. G., Van Winkle, M., Ind. Eng. Chem. Process Des. Develop.
(1968) 7, 213.
10. Tassios, D. P., Hydrocarbon Process. (1970) 49, 7, 144.
11. Tassios, D. P., Ind. Eng. Chem. Process Des. Develop. (1972) 11, 43.
12. Furter, W. F., Cook, R. ., Int.J.Heat Mass Transfer (1967) 10, 23.
13. Wilson, G. M.,J.Amer. Chem. Soc. (1964) 86, 127.
14. Renon, H., Prausnitz, J. M., A.I.Ch.E.J.(1968) 14, 135.
15. Marina, J., Dissertation, Newark College of Engineering, Newark, 1972b.
16. Marina, J., Tassios, D. P., Ind. Eng. Chem. Process Des. Develop., in
press.
17. Larson, C. D., Tassios, D. P., Ind. Eng. Chem. Process Des. Develop.
(1972) 11, 35.
18. Hankinson, R. W., Langfitt, B. D., Tassios, D. P., Can. J. Chem. Eng., in
press.
19. Tassios, D. P., A.I.Ch.E. J. (1971) 17, 1367.
20. Taques, D., Furter, W. F., Advan. Chem. Ser. (1972) 115, 159.
21. Marina, J., Tassios, D. P., Ind. Eng. Chem. Process Des. Develop., sub
mitted for publication.
22. O'Connell, J., Prausnitz, T. M., Ind. Eng. Chem. Process Des. Develop.
(1967) 6, 245.
23. Robinson, C. S., Gilliland, E. R., "Elements of Fractional Distillation,"
p. 312, McGraw-Hill, New York, 1950.
24. Hoffman, E. S., "Azeotropic and Extractive Distillation," Wiley, New York,
1964.
25. Black, C., Golding, R. ., Ditsler, D. E., ADVAN. CHEM. SER. (1972) 115,
64.
26. Amudson, N. R., Pontinen, A. J., Ind. Eng. Chem. (1958) 50, 730.
27. Naphthali, L. M., 56th A.I.Ch.E. Meet., San Francisco (May 1965).
28. Bruno, J. ., Yanosik, J. L., Tierney, J. W., ADVAN. CHEM. SER. (1972)
115, 122.
29. Black, C., Ditsler, D. E., ADVAN. CHEM. SER. (1972) 115, 1.
30. Gerster, J. ., Chem. Eng. Progr. (1969) 65, 9, 43.
xi
1
Dehydration of Aqueous Ethanol Mixtures
by Extractive Distillation
C. BLACK and D. E. DITSLER
Shell Development Co., Emeryville, Calif. 94608
Although nonidealities in vapor and liquid phases complicate

the separation of components from mixtures, a knowledge of
these nonidealities can be applied to design an extractive
distillation step. Ethylene glycol is added to an aqueous
ethanol mixture to produce the overhead separation of ethanol from water. Methods published earlier by one of the
authors are applied to calculate phase equilibria in a computer calculation of the separation. The extractive distillation results are tabulated, represented graphically, and
discussed to illustrate extractive distillation as a method for
dehydrating aqueous ethanol mixtures. The results are compared with corresponding results obtained by azeotropic
distillation with n-pentane as entrainer. They show extractive distillation with ethylene glycol is more expensive than
azeotropic distillation with n-pentane.
C e p a r a t i n g c o m p o n e n t s f r o m m i x t u r e s is c o m p l i c a t e d b y n o n i d e a l i t i e s i n
^
the l i q u i d a n d v a p o r phases. N e v e r t h e l e s s , a k n o w l e d g e o f t h e factors
c o n t r i b u t i n g to the n o n i d e a l i t y of the m i x t u r e s h e l p s to p r o d u c e a j u d i c i o u s
d e s i g n for the s e p a r a t i o n step. S o m e t i m e s c o m p o n e n t s are a d d e d t o the
m i x t u r e to alter the n o n i d e a l i t y b y c h a n g i n g the m o l e c u l a r e n v i r o n m e n t .
E x t r a c t i v e d i s t i l l a t i o n is u s e d because the c o m p o n e n t s are d i s t r i b u t e d
differently b e t w e e n c o n t a c t i n g l i q u i d a n d v a p o r phases i n e q u i l i b r i u m
w h e n a h i g h - b o i l i n g n o n i d e a l c o m p o n e n t is a d d e d to the m i x t u r e .
The
a d d e d c o m p o n e n t is i n t r o d u c e d i n the u p p e r p a r t of a d i s t i l l a t i o n c o l u m n
a b o v e the f e e d a n d r e m a i n s i n a p p r e c i a b l e c o n c e n t r a t i o n i n the l i q u i d o n
a l l of the l o w e r trays.
It is r e m o v e d f r o m the c o l u m n w i t h one of the
c o m p o n e n t s b e i n g separated as t h e bottoms p r o d u c t . A l t h o u g h a n o n i d e a l
c o m p o n e n t is also i n t r o d u c e d for a z e o t r o p i c d i s t i l l a t i o n , t h e a d d e d c o m 1
E X T R A C T I V E
Table I.
A N D
DISTILLATION
Constants for Calculating Imperfection-Pressure Coefficients

E'
0.089
0.089
0.026
4.75
4.75
4.75
75.9
79.2
24.7
P ,Atm.
c
Ethanol
Ethylene glycol
Water
A Z E O T R O P I C
516.3
761.11
647.00
63.1
84.04
218.0
11 coefficients have been taken equal to zero.
p o n e n t is, i n that case, m o r e easily v o l a t i l i z e d f r o m t h e m i x t u r e t h a n one

of the c o m p o n e n t s b e i n g separated. C o n s e q u e n t l y i t is r e m o v e d o v e r h e a d
from the column.
I n either case the r e l a t i v e d i s t r i b u t i o n s b e t w e e n t h e s e p a r a b l e l i q u i d
a n d v a p o r phases are p r e d i c t e d f r o m t h e p u r e c o m p o n e n t v a p o r pressures
Pi,
l i q u i d p h a s e a c t i v i t y coefficients, /s, a n d i m p e r f e c t i o n - p r e s s u r e co
efficients 0/s.
U s i n g these three q u a n t i t i e s , the r e l a t i v e d i s t r i b u t i o n is
expressed as
y*Pifl,
E x t r a c t i v e d i s t i l l a t i o n has b e e n extensively u s e d for n e a r l y

decades i n l a b o r a t o r y , p i l o t p l a n t , a n d c o m m e r c i a l p l a n t operations.
three
Cal
c u l a t i o n or p r e d i c t i o n of p h a s e e q u i l i b r i a for s u c h separations has often

b e e n d i s c u s s e d ( I , 2, 3 ) .
S o m e h a v e d i s c u s s e d t h e selection of solvents
f o r e x t r a c t i v e d i s t i l l a t i o n (4, 5 ) .
O t h e r s h a v e d i s c u s s e d its r e c e n t a p p l i
c a t i o n t o p a r t i c u l a r separations (6, 7, 8 ) .
A c o m p a r i s o n of
extractive
d i s t i l l a t i o n , as a s e p a r a t i o n m e t h o d , w i t h a z e o t r o p i c d i s t i l l a t i o n a n d w i t h
l i q u i d - l i q u i d e x t r a c t i o n has r e c e n t l y b e e n d i s c u s s e d briefly b y G e r s t e r
(9).
T h e use of d i g i t a l c o m p u t e r s to c a r r y o u t c o m p l e t e c a l c u l a t i o n s i n
the d e s i g n of s e p a r a t i o n processes has b e e n the g o a l of m a n y . T o d o this
effectively, s u i t a b l e m e t h o d s for p h a s e e q u i l i b r i a a n d tray-to-tray d i s
t i l l a t i o n c a l c u l a t i o n s are r e q u i r e d . R e s u l t s c a l c u l a t e d b y t h e a p p l i c a t i o n
of s u c h m e t h o d s to d e h y d r a t e a q u e o u s e t h a n o l m i x t u r e s u s i n g e t h y l
ene g l y c o l as the extractive d i s t i l l a t i o n solvent is d i s c u s s e d b e l o w .
b r i e f r e v i e w of t h e m e t h o d s u s e d for p h a s e e q u i l i b r i a a n d e n t h a l p i e s is
f o l l o w e d b y a d i s c u s s i o n of t h e results f r o m d i s t i l l a t i o n c a l c u l a t i o n s . T h e s e
are c o m p a r e d for extractive d i s t i l l a t i o n w i t h c o r r e s p o n d i n g results o b
t a i n e d b y a z e o t r o p i c d i s t i l l a t i o n w i t h n-pentane.
Phase
Equilibria
T h e i m p o r t a n t q u a n t i t i e s n e e d e d to represent the n o n i d e a l p h a s e
e q u i l i b r i a for extractive d i s t i l l a t i o n are v a p o r pressures *, l i q u i d - p h a s e
a c t i v i t y coefficients
y% a n d i m p e r f e c t i o n - p r e s s u r e
coefficients

ft.
The
1.
B L A C K
A N D
Dehydration
DITSLER
Table II.
of Ethanol
Constants for Vapor Pressure Equations

A
Ethanol
Ethylene glycol
Water
a
Mixtures
8.16280
7.71147
20.844*
Antoine equations.
Log = A - BIT -
C
1623.22
1816.34
2817.4*
228.98
178.603
4.04859*
C log ; P, mm Hg, T , K.
c r i t i c a l constants a n d other coefficients for c a l c u l a t i n g the i m p e r f e c t i o n pressure coefficients (1)
are g i v e n i n T a b l e I. E q u a t i o n s a n d coefficients
for c a l c u l a t i n g v a p o r pressures are g i v e n i n T a b l e II.
As binary vapor
i n t e r a c t i o n s h a v e b e e n neglected, the values for t h e *, coefficients
have
a l l b e e n t a k e n e q u a l to z e r o as s h o w n i n T a b l e I.
T h e M o d i f i e d v a n L a a r equations ( I )
t h e l i q u i d phase a c t i v i t y coefficients.
are g i v e n i n T a b l e III.
h a v e b e e n u s e d to c a l c u l a t e
Coefficients at three
temperatures
T h e s e are u s e d b y t h e c o m p u t e r to c a l c u l a t e ac
t i v i t y coefficients at a n y c o m p o s i t i o n a n d t e m p e r a t u r e i n the d i s t i l l a t i o n
column.
E n t h a l p i e s for s a t u r a t e d l i q u i d s a n d v a p o r s are g i v e n i n T a b l e
for the p u r e c o m p o n e n t s r e f e r r e d to z e r o for t h e l i q u i d s at 32 F .
IV
Vapor
m i x t u r e s are c a l c u l a t e d a s s u m i n g z e r o heat of m i x i n g . L i q u i d e n t h a l p i e s
for the m i x t u r e s are c a l c u l a t e d to i n c l u d e t h e i n t e g r a l heat of m i x i n g ,
g i v e n a c c o r d i n g to
(2)
H^^îU),
w h e r e t h e differential heat of m i x i n g (Li)
(L). =
Table III.
is g i v e n as
2.303#( l o g < ) . / ( 1 / )
(3)
Modified van Laar Coefficients for the System

Ethanol-Ethylene G l y c o l - W a t e r
Binary %
Ethanol-ethylene glycol
Ethanol-water
Ethylene gly col-water
Ethanol-water
E t h y l e n e glycolwater
Ethanol-water
Ethylene glycol-water
Ai,
0.276000
0.728000
0.001680
0.251000
0.74600
0.00142
0.23000
0.76050
0.00130
0.259279
0.407000
0.001000
0.23579
0.40080
0.00081
0.21607
0.39250
0.000714
0.000000
0.000000
0.000000
0.000000
0.000000
0.000000
0.000000
0.000000
0.000000

t,C
75.0
75.0
75.0
87.8
87.8
87.8
100.0
100.0
100.0
E X T R A C T I V E
Table IV.
Ethylene
glycol
Water
Distillation
A Z E O T R O P I C
DISTILLATION
Enthalpies for Liquid and Vapor

h
(liquid)
Btu/lb.
mole
t F
Ethanol
A N D
H ( vapor)
Btu/lb.
mole
32
100
200
300
0.00
2506.1
6034.9
10365.3
19800.0
20937.9
22573.3
23969.2
100
200
300
400
3637.0
7535.0
11600.0
15889.0
30724.0
32828.0
35193.0
37700.0
100
200
300
1225.0
3027.0
4820.0
19916.0
20649.0
21290.0
Calculations
C a l c u l a t i o n s for t h e extractive d i s t i l l a t i o n o f aqueous e t h a n o l m i x

tures c o n t a i n i n g 8 5 . 6 4 % m e t h a n o l h a v e b e e n c a r r i e d o u t w i t h t h e a i d of
a U N I V A C 1108 c o m p u t e r .
T h e c o m p u t e r p r o g r a m calculates a l l p h a s e
e q u i l i b r i a a n d tray-to-tray m a t e r i a l a n d heat balances for e a c h c o m p o n e n t
250
,71.43%
<
LU
eg
LU
200
S/F = 2.5 (MOLE)
150
y
75%
100 h
^^77.78%
50
-
:
.0
Figure I .
99%
1
1.8
,
2.6
R/F (MOLE BASIS)
80%
1
3.4
Effects on product purity of changing solvent-feed

feea ratios
and reflux-
recovery of ethanol in the extractive distilfotion with ethylene glycol at

14.7 psia

1.
B L A C K
A N D
2
Figure 2.
DITSLER
Dehydration
of Ethanol
Mixtures
3
4
ETHYLENE GLYCOL/ANOL (MOLE BASIS)
Effect of solvent-feed ratio on product purity in the
distillation of aqueous ethanol with ethylene glycol
5
extractive
i n the feed. F o r fixed e t h y l e n e - g l y c o l f e e d ratios c a l c u l a t i o n s w e r e m a d e

for a n e t h a n o l r e c o v e r y of 9 9 % m i n the o v e r h e a d at f o u r different r e f l u x f e e d ratios i n the r a n g e 1-
m o l e basis. E a c h series o f c a l c u l a t i o n s w a s
m a d e at the constant s o l v e n t - f e e d
ratios o f 2.5, 3.0, 3.5, a n d 4.0 m o l e
basis. T h e pressure d r o p p e r tray w a s a s s u m e d t o b e 0.1 p s i w i t h the

r e b o i l e r pressure set a t 14.7 p s i a .
A drop o f two psi from top tray t o
condenser w a s a s s u m e d for t h e c a l c u l a t i o n . T h e reflux t e m p e r a t u r e w a s

set at 104.0F. A t o t a l of 46 trays w i t h solvent a d d e d o n 43 a n d f e e d at
t r a y 2 2 w a s u s e d for the c a l c u l a t i o n s . T h e f e e d a n d t h e solvent w e r e
i n t r o d u c e d as l i q u i d at 110 a n d 173F, respectively.
T h e s e results h a v e b e e n u s e d to s h o w the effects o f c h a n g i n g r e f l u x f e e d r a t i o at fixed values of the s o l v e n t - f e e d ratio. I n F i g u r e 1 the w a t e r
i n t h e e t h a n o l p r o d u c t is p l o t t e d vs. t h e r e f l u x - f e e d r a t i o , b o t h expressed
o n a m o l e basis. F o u r curves are s h o w n , e a c h r e p r e s e n t i n g a different
solvent-feed
ratio. E a c h c u r v e goes t h r o u g h a m i n i m u m as the r e f l u x -
f e e d r a t i o changes.
pronounced.
A t low solvent-feed
A t high solvent-feed
ratios t h e m i n i m u m i s m o r e
ratios i t i s s h a l l o w , s h o w i n g
only
s m a l l changes as t h e r e f l u x - f e e d varies f r o m 1.4-1.8, m o l e basis.

A t the r e f l u x - f e e d
r a t i o o f 1.5545 t h e w a t e r
content o f the
top
p r o d u c t , e t h a n o l , is near the m i n i m u m for e a c h s o l v e n t - f e e d r a t i o s h o w n .

F o r this r e f l u x - f e e d r a t i o , t h e w a t e r content o f the t o p p r o d u c t has b e e n
p l o t t e d vs. the ethylene g l y c o l - e t h a n o l ratios i n F i g u r e 2.
This curve

E X T R A C T I V E
A N D
A Z E O T R O P I C
DISTILLATION
24
REBOILER
20
16
CONDENSER
12
8
4
ETHYLENE GLYCOL/ETHANOL RATIO, MOLES
3
Reboiler and condenser heat loads vs. solvent-feed
Figure 3.
99%
ratio
recovery of ethanol, feed rate 242.02 moles ethanol/hour reflux/feed = 1.5545

mole basis
defines the w a t e r c o n t e n t o f the e t h a n o l p r o d u c t as a f u n c t i o n o f t h e

solvent-ethanol ratio.
If the f e e d rate is fixed at 242.02 moles o f e t h a n o l p e r h o u r a n d t h e
heat loads for r e b o i l e r a n d condenser are c a l c u l a t e d , t h e effect o f c h a n g i n g
s o l v e n t - e t h a n o l r a t i o c a n b e o b t a i n e d . T h e s e results are s h o w n i n F i g u r e
3.
Since ethanol is recovered
a t 9 9 % m o l e i n e a c h case a n d t h e
Table V .
Extractive Distillation Column
Ethanol-Ethylene G l y c o l - W a t e r at 14.7 Psia
Material
Components
Feed/Moles
top
Balance
Solvent/Moles
Top
Product
Moles
Bottom
Product
Moles
Ethanol
Ethylene glycol
Water
0.8564
0.0000
0.1436
3.5000
0.856315
0.000001
0.000014
0.000085
3.499999
0.143586
Totals
1.000
3.5000
0.856330
3.643670
"Reboiler load 73,969 Btu/unit time, top load 46,433 Btu/unit time.
* Liquid feed at 110F on tray 22, liquid solvent at 173F on tray 43.

1.
B L A C K
A N D
Dehydration
DITSLER
of Ethanol
Mixtures
Table VI.
Extractive Distillation Column
Temperature,
Tray
No.
Condenser
46
44
43
42
40
38
36
34
32
30
28
26
24
22
20
18
16
14
12
10
8
6
4
2
1
Composition,
and Volatility
Profiles
t, F
Ethanol
in
Vapor, Mole
Fraction
Water in
Liquid,
Mole
Fraction
psia
a
W/E
104.0
156.9
158.7
195.3
195.8
196.6
197.5
198.4
199.2
200.0
200.9
201.7
202.7
203.7
194.8
195.5
196.3
197.0
197.7
198.5
199.5
202.0
218.5
246.2
297.9
362.1
0.999983
0.999984
0.999793
0.987189
0.987120
0.98696
0.98677
0.98648
0.98601
0.98517
0.98356
0.98037
0.97395
0.96087
0.93873
0.93854
0.93827
0.93772
0.93615
0.93079
0.91132
0.83701
0.53735
0.07283
0.00349
0.00054
0.000016
0.000015
0.000013
0.000011
0.000019
0.00005
0.00011
0.00024
0.00051
0.00107
0.00220
0.00454
0.00934
0.01926
0.04539
0.04546
0.04561
0.04600
0.04731
0.05201
0.06951
0.13805
0.35352
0.46407
0.19499
0.03941
8.20
10.20
10.4
10.5
10.6
10.8
11.0
11.2
11.4
11.6
11.8
12.0
12.2
12.4
12.6
12.8
13.0
13.2
13.4
13.6
13.8
14.0
14.2
14.4
14.6
14.6
1.11
1.09
0.485
0.486
0.488
0.489
0.490
0.492
0.493
0.493
0.492
0.489
0.482
0.532
0.533
0.534
0.535
0.535
0.532
0.516
0.452
0.274
0.208
0.311
0.428
p r o d u c t is a l w a y s h i g h p u r i t y e t h a n o l , the t o p l o a d for the
condenser
r e m a i n s n e a r l y constant. T h e r e b o i l e r l o a d , h o w e v e r , reflects the c h a n g e

as t h e s o l v e n t - e t h a n o l r a t i o varies.
C h a n g i n g the r e c o v e r y of e t h a n o l f r o m 9 9 - 9 9 . 9 9 % m p r o d u c e s o n l y
m i n o r increases i n t h e heat loads.
A s u m m a r y of the c o l u m n m a t e r i a l
b a l a n c e for one m o l e of feed is s h o w n i n T a b l e V w h e n t h e

r a t i o is 3.5 m o l e basis.
solvent-feed
T h i s c a l c u l a t i o n w a s m a d e for a r e c o v e r y
of
9 9 . 9 9 % m e t h a n o l u s i n g 46 e q u i l i b r i u m trays w i t h t h e solvent o n 43 a n d
t h e f e e d o n 22. T h e r e f l u x - f e e d r a t i o w a s 1.5537 m o l e basis. T h e corre
s p o n d i n g d a t a for t e m p e r a t u r e , c o m p o s i t i o n , a n d v o l a t i l i t y profiles
summarized in Table VI.

are
E X T R A C T I V E
Figure 4.
99.99%
Temperature
A N D
A Z E O T R O P I C
DISTILLATION
profile in extractive distillation of aqueous
recovery of ethanol, ethylene glycol/ethanol

feed 1.5537 moles
ratio =
ethanol
4.08688 moles, reflux-
NUMBER OF TRAYS (EQUIL.)

Figure
5.
EG/
Volatility
=
profiles in the extractive distillation

ethanol with ethylene glycol
4.08688, R/F
of
aqueous
1.5537 moles, 99.99% recovery, ethanol

1.
B L A C K
A N D
DITSLER
Dehydration
of Ethanol
Mixtures
T h e t e m p e r a t u r e profile for the extractive d i s t i l l a t i o n results of T a b l e

V I has b e e n p l o t t e d i n F i g u r e 4.
T h e h i g h solvent i n p u t t e m p e r a t u r e
a n d the l o w f e e d i n p u t t e m p e r a t u r e cause s l i g h t l y h i g h e r
temperatures
i n m u c h m o r e of the r e c t i f y i n g section t h a n i n the u p p e r p a r t of
the
s t r i p p i n g section. T h e c o r r e s p o n d i n g v o l a t i l i t y profile for t h e c o l u m n is

s h o w n i n F i g u r e 5. T h e i n d i v i d u a l values are also s h o w n there. A s t h e
t e m p e r a t u r e increases u p o n a p p r o a c h i n g t h e r e b o i l e r , the r e l a t i v e v o l a
t i l i t y for w a t e r w i t h respect to e t h a n o l w o u l d decrease i f t h e
solvent
c o n c e n t r a t i o n r e m a i n e d fixed. H o w e v e r t h e ethylene g l y c o l c o n c e n t r a t i o n
i n the l i q u i d increases, t e n d i n g t o m a k e t h e r e l a t i v e v o l a t i l i t y increase.
These
two
opposing
influences m a k e the r e l a t i v e v o l a t i l i t y c u r v e
go
t h r o u g h a m i n i m u m n e a r t r a y n u m b e r four, as seen i n F i g u r e 5.
MOLE FRACTION
Figure
EG/
6.
=
Composition
profiles in the extractive distillation
aqueous ethanol with ethylene glycol
4.08688 moles, R/F
of
= 1.5537 moles, 99.99% recovery

ethanol
C o m p o s i t i o n profiles for the same extractive d i s t i l l a t i o n c o l u m n are

s h o w n i n F i g u r e 6. T h e w a t e r c o n c e n t r a t i o n i n the l i q u i d goes t h r o u g h
a p r o n o u n c e d m a x i m u m at a b o u t t r a y n u m b e r f o u r (see
T a b l e V I ) , cor
r e s p o n d i n g to t h e m i n i m u m i n the relative v o l a t i l i t y of w a t e r w i t h respect

to e t h a n o l . I n this r e g i o n the e t h a n o l c o n c e n t r a t i o n i n t h e v a p o r increases
r a p i d l y , c h a n g i n g f r o m less t h a n 2 % at tray n u m b e r three to m o r e t h a n
50%
at t r a y n u m b e r six. T h i s r a p i d increase c o n t i n u e s to a b o u t t r a y
n u m b e r t e n w h e r e the c o n c e n t r a t i o n of e t h a n o l i n t h e v a p o r is a b o u t

10
E X T R A C T I V E
91 %m.
A N D
A Z E O T R O P I C
DISTILLATION
W a t e r d r o p s o u t of the v a p o r i n the r e c t i f y i n g section b e t w e e n
the f e e d t r a y a n d the solvent i n p u t t r a y w h i l e e t h a n o l c o n t i n u e s
to
concentrate.
A b o v e the solvent i n l e t the ethylene g l y c o l d r o p s out r a p i d l y , so i n
three e q u i l i b r i u m trays it is r e d u c e d f r o m a b o u t 1.3% m to less t h a n 2
p p m . T h e w a t e r content of the t o p p r o d u c t , e t h a n o l , is a b o u t 16 p p m o n
a m o l e basis, as c a l c u l a t e d f r o m the results of T a b l e V .
T h e b o t t o m p r o d u c t f r o m the extractive d i s t i l l a t i o n c o l u m n is aqueous
ethylene g l y c o l w i t h 3 . 9 4 % m water.
T h i s is f e d to a solvent r e c o v e r y
c o l u m n w h e r e w a t e r is s t r i p p e d f r o m the e t h y l e n e g l y c o l w h i c h is t h e n
r e c y c l e d as solvent to the extractive d i s t i l l a t i o n c o l u m n .
C a l c u l a t e d results for the solvent r e c o v e r y c o l u m n w i t h n i n e t o t a l
trays h a v i n g the f e e d i n l e t o n tray five are g i v e n i n T a b l e V I I .
T h e re
b o i l e r pressure has b e e n t a k e n as 14.7 p s i a . T h e pressure d r o p p e r tray

has b e e n set at 0.09 p s i . A d r o p of 1.7 p s i f r o m t h e t o p tray to the c o n Table VII.
Solvent Recovery Column
Temperature
Tray
No.
10 C o n d .
9 Top
8
7
6
5 Feed
4
3
2
1 Reboiler
t,
and Composition
Water in
Vapor, Mole
Fraction
Ethylene
Glycol
in Liquid,
Mole
Fraction
psia
a
EG/W
0.99936
0.99936
0.99830
0.93928
0.42680
0.15285
0.04343
0.01103
0.00265
0.00056
.00004
.00176
.06686
.64743
.95536
.98755
.99763
.99919
.99981
.99996
12.28
13.98
14.07
14.16
14.25
14.34
14.43
14.52
14.61
14.70
.0216
.0224
.0352
.0627
.0699
.0723
.0731
.0734
.0736
104.0
209.5
213.3
264.6
356.8
379.6
387.6
390.2
391.1
391.7
Material
Components
Profiles
FeedMoles
Balance
Top Product
Moles
Bottom
Product
Ethanol
Ethylene glycol
Water
0.000085
3.499999
0.143586
.000085
.000006
.143442
.000000
3.499993
0.000144
Totals
3.643670
.143533
3.500137
R e b o i l e r l o a d 3,3015 B t u / U n i t
Top load
2,8709 B t u / U n i t
Moles
Time
Time
Based on one mole of feed to the extractive distillation column which precedes
the solvent recovery column.
a

1.
B L A C K
A N D
Figure
DITSLER
7.
Dehydration
Temperature
of Ethanol
11
Mixtures
profile for solvent recovery
column
Stripping water from aqueous ethylene glycol
denser has b e e n a s s u m e d . T h e reflux t e m p e r a t u r e w a s set at 104 F a n d

t h e r e f l u x - f e e d r a t i o at 1.33491, m o l e basis. T h e f e e d t e m p e r a t u r e w a s
358 F , a f e w degrees less t h a n the b o t t o m t e m p e r a t u r e of the extractive
d i s t i l l a t i o n c o l u m n . M a t e r i a l b a l a n c e a n d c o l u m n profiles are g i v e n i n
T a b l e V I I for the r e c o v e r y c o l u m n .
T h e t e m p e r a t u r e profile for this c o l u m n is s h o w n i n F i g u r e 7.
The
c o m p o s i t i o n profiles are p l o t t e d i n F i g u r e 8. T h e s e s h o w the e x p e c t e d

trends, w a t e r i n the v a p o r i n c r e a s i n g a n d e t h y l e n e g l y c o l i n the l i q u i d
d e c r e a s i n g as one proceeds f r o m the r e b o i l e r to t h e t o p of the c o l u m n .
W i t h t h e n u m b e r of trays s h o w n a n d the r e f l u x - f e e d r a t i o g i v e n , e t h y l e n e
g l y c o l i n the t o p p r o d u c t ( w a t e r ) is r e d u c e d to a b o u t 42 p p m , m o l e basis.
E t h a n o l i n the w a t e r p r o d u c t is a b o u t 0 . 0 6 % m .
R e d u c i n g e t h y l e n e g l y c o l i n the w a t e r p r o d u c t to a s i g n i f i c a n t l y l o w e r
v a l u e r e q u i r e s o n l y the a d d i t i o n of one or m o r e r e c t i f y i n g trays i n t h e
recovery
c o l u m n . A n increase i n the r e f l u x - f e e d
r a t i o w i l l d o as a n
alternate m e t h o d , b u t to c h a n g e t h e e t h a n o l i n the w a t e r p r o d u c t , the

extractive d i s t i l l a t i o n c o l u m n w o u l d h a v e to b e o p e r a t e d for h i g h e r or
l o w e r e t h a n o l r e c o v e r y t h a n the 9 9 . 9 9 % m v a l u e . T h i s c a n b e d o n e w i t h o u t difficulty.
T h e b o t t o m p r o d u c t f r o m the solvent r e c o v e r y c o l u m n is e t h y l e n e
g l y c o l w i t h a b o u t 41 p p m of w a t e r , m o l e basis. B y c h a n g i n g the n u m b e r
of s t r i p p i n g trays i n the solvent r e c o v e r y c o l u m n , this w a t e r c o n t e n t c a n
r e a d i l y be d e c r e a s e d or i n c r e a s e d .

12
E X T R A C T I V E
A N D
A Z E O T R O P I C
DISTILLATION
I f t h e t o p p r o d u c t ( w a t e r ) f r o m t h e solvent r e c o v e r y c o l u m n is to
be discarded, the two distillation columns w o u l d be operated to reduce
e t h a n o l a n d e t h y l e n e g l y c o l to l o w c o n c e n t r a t i o n s , as i l l u s t r a t e d i n the
c a l c u l a t i o n s s h o w n here.
H o w e v e r , w h e r e the o v e r a l l p l a n t s c h e m e is
s u c h t h a t t h e w a t e r p r o d u c t m i g h t b e r e c y c l e d a n d usede.g>, as solvent
to a n a q u e o u s extractive d i s t i l l a t i o n , i t m i g h t u n d e r some c o n d i t i o n s b e
m o r e e c o n o m i c a l to leave m o r e e t h a n o l i n the w a t e r p r o d u c t . T h e e t h a n o l
w o u l d b e r e c o v e r e d i n the series of s e p a r a t i o n steps w h i c h f o l l o w i n the
flow
scheme. W a t e r m i g h t b e rejected at a m o r e s u i t a b l e p o i n t i n the
flow s c h e m e t h a n f r o m the t o p of the solvent r e c o v e r y c o l u m n . T h e best

o p e r a t i n g c o n d i t i o n s c a n b e d e t e r m i n e d o n l y w h e n the e n t i r e p l a n t
flow
scheme is k n o w n .
Comparison of Extractive
with Azeotropic
Distillation
A l t h o u g h e t h a n o l is o b t a i n e d as a t o p p r o d u c t f r o m a n extractive
d i s t i l l a t i o n w i t h e t h y l e n e g l y c o l , it is o b t a i n e d as a b o t t o m p r o d u c t f r o m
a n a z e o t r o p i c d i s t i l l a t i o n c o l u m n u s i n g a n entraner s u c h as n-pentane.
B a s e d o n a n e t h a n o l rate of 242.02 moles p e r h o u r , a r o u g h c o m p a r i s o n
w i l l b e m a d e of the t w o s e p a r a t i o n m e t h o d s .
CONDENSER 10
MOLE FRACTION
Figure
8.
Composition
profiles for solvent recovery
column
Stripping water from aqueous ethylene glycol

1.
B L A C K
A N D
DITSLER
Table VIII.
Dehydration
Distillation,
14.7
Ethanol
psia
(85.64%m
Azeotropic
13
Mixtures
Comparing Extractive and Azeotropic
Feed: Aqueous
Extractive
of Ethanol
Distillation
Ethanol)
Distillation,
50 psia
S o l v e n t = ethylene g l y c o l
M o l e s s o l v e n t - e t h a n o l = 4.08688
R e f l u x - f e e d r a t i o = 1.55369
46 T r a y s t o t a l i n e x t r a c t i v e d i s t . c o l .
S o l v e n t o n t r a y 43
F e e d on t r a y 22
R e b o i l e r l o a d = 20.9 m i l l i o n
Btu/hour
T o p l o a d = 13.12 m i l l i o n
Btu/hour
T o w e r d i a m e t e r = 5.3 feet
Ethanol product:
W a t e r 16 p p m (mole basis)
S o l v e n t 1.2 p p m (mole basis)
E t h a n o l recovery f r o m feed =
99.99%
Entraner = n-pentane
Moles n-pentane-ethanol =
S o l v e n t recovery c o l u m n
9 T r a y s , R / F = 1.33491 (mole)
R e f l u x on t r a y 9
Feed on t r a y 5
Btu/hour
T o p l o a d = 8.11 m i l l i o n
Btu/hour
T o w e r d i a m e t e r = 4.1 feet
Stripping column
T o t a l heat to reboilers = 30.23

million Btu/hour
T o t a l t o p loads = 21.23 m i l l i o n
Btu/hour
T o t a l heat t o reboilers < 13 m i l l i o n

Btu/hour
T o t a l t o p loads < 14 m i l l i o n
Btu/hour
3.214
18 T r a y s t o t a l i n azeotropic dist. c o l .
Entraner o n t r a y 18
F e e d o n t r a y 16
Btu/hour
C o n d e n s e r l o a d 11.33 m i l l i o n
Btu/hour
T o w e r d i a m e t e r < 5 feet
Ethanol product:
W a t e r < 3 p p m ( m o l e basis)
n - P e n t a n e < 1 p p m (mole basis)
E t h a n o l r e c o v e r y f r o m feed
>99.99%
Reboiler load <2. million

Btu/hour
Top load <2. million Btu/hour
T o w e r d i a m e t e r < 2 . feet
"Based on 242.02 moles/hour of ethanol in feed to plant.
F o r the extractive d i s t i l l a t i o n results of T a b l e s V a n d V I , the r e b o i l e r

l o a d for the a b o v e e t h a n o l rate w o u l d b e a b o u t 20.9 m i l l i o n B t u p e r h o u r .
T h e e t h a n o l p r o d u c t contains a b o u t 16 p p m of w a t e r a n d a b o u t 1.2 p p m
of ethylene g l y c o l . F o r a n e t h a n o l r e c o v e r y of 9 9 . 9 9 % ra, 46 t o t a l e q u i
l i b r i u m trays are r e q u i r e d w i t h a r e f l u x - f e e d r a t i o of 1.55 a n d a s o l v e n t +
e t h a n o l r a t i o of 4.09' m o l e basis. T h e condenser l o a d is a b o u t 13.1 m i l l i o n

B t u / h o u r , a n d the t o w e r d i a m e t e r is a b o u t 5.3 feet, b a s e d o n a G l i t s c h
sizing technique.

14
E X T R A C T I V E
A N D
A Z E O T R O P I C
DISTILLATION
I f n-pentane is selected as the entraner for a n a z e o t r o p i c d i s t i l l a t i o n

scheme, a n e t h a n o l p r o d u c t c o n t a i n i n g less w a t e r t h a n that o b t a i n e d i n
the extractive d i s t i l l a t i o n m e t h o d is easily o b t a i n e d w i t h e n t r a i n e r - e t h a n o l ratios of 2.5-3.5, m o l e basis (10).
F o r a r a t i o of 3.214, t h e w a t e r
c o n t e n t of the e t h a n o l is less t h a n 3 p p m . O n l y 18 e q u i l i b r i u m trays are

r e q u i r e d i n a c o l u m n of less t h a n 5 feet diameter.
T h e heat loads i n
m i l l i o n s B t u / h o u r are a b o u t 10.7 for the r e b o i l e r a n d 11.3 for t h e c o n denser.
A s t r i p p e r is u s e d to recover n-pentane a n d e t h a n o l f r o m the
a q u e o u s phase. T h e r e c o v e r e d n-pentane a n d e t h a n o l c a n b e r e c y c l e d
either to the f e e d or to t h e reflux stream of the a z e o t r o p i c d i s t i l l a t i o n
column.
T h e s t r i p p e r r e q u i r e d to process the aqueous p h a s e for r e c o v e r i n g
n-pentane a n d e t h a n o l r e q u i r e s a f e w m o r e trays, b u t i t has a c o l u m n
d i a m e t e r less t h a n h a l f that of the solvent r e c o v e r y c o l u m n for the extract i v e d i s t i l l a t i o n scheme. T h e heat loads are also m u c h smaller. T h e t o p
p r o d u c t , c o n s i s t i n g of n-pentane, e t h a n o l , a n d some w a t e r , is r e c y c l e d
to t h e reflux stream of the extractive d i s t i l l a t i o n c o l u m n .
T h e results of c a l c u l a t i o n s for the t w o s e p a r a t i o n m e t h o d s are s u m marized in Table VIII.
F e w e r trays are r e q u i r e d i n t h e a z e o t r o p i c dis-
t i l l a t i o n c o l u m n t h a n the extractive d i s t i l l a t i o n c o l u m n . T h e heat loads

are also smaller. T h e q u a l i t y of the e t h a n o l p r o d u c t is also s l i g h t l y better
for the a z e o t r o p i c d i s t i l l a t i o n m e t h o d . I n c l u d i n g t h e s t r i p p e r for processi n g the aqueous phase, the t o t a l heat l o a d for reboilers for the a z e o t r o p i c
d i s t i l l a t i o n m e t h o d is less t h a n h a l f that for the extractive d i s t i l l a t i o n
method.
T h e t o t a l c o n d e n s e r l o a d is r o u g h l y t w o - t h i r d s t h a t for
the
extractive d i s t i l l a t i o n m e t h o d .
A l t h o u g h the a z e o t r o p i c d i s t i l l a t i o n scheme, u s i n g n-pentane, operates at a h i g h e r pressure, c o m p a r a t i v e c a l c u l a t i o n s i n d i c a t e this t o b e
better t h a n the extractive d i s t i l l a t i o n scheme u s i n g d i e t h y l e n e g l y c o l to
dehydrate aqueous ethanol.
List of Symbols
H
(Li)a-
the i n t e g r a l heat of m i x i n g for m i x t u r e of c o m p o s i t i o n

the differential heat of m i x i n g f o r c o m p o n e n t i at c o m p o s i t i o n
Pi
v a p o r pressure for c o m p o n e n t i
P,-
v a p o r pressure for c o m p o n e n t /
v o l a t i l i t y of c o m p o n e n t i r e l a t i v e to c o m p o n e n t /
l i q u i d p h a s e a c t i v i t y coefficient for c o m p o n e n t i
jj
l i q u i d phase a c t i v i t y coefficient for c o m p o n e n t /
i m p e r f e c t i o n - p r e s s u r e coefficient for c o m p o n e n t i
6j
i m p e r f e c t i o n - p r e s s u r e coefficient for c o m p o n e n t /

1. BLACK AND DITSLER
Dehydration of Ethanol Mixtures
15
Literature Cited
1. Black, C., Derr, E. L., Papadopoulos, M. N., Ind. Eng. Chem. (1963) 55,
No. 9, 38-47.
2. Garner, F. H., Ellis, S. R. M., Trans. Inst. Chem. Eng. (London) (1951)
29, 45.
3. Null, H. R., Palmer, D. ., Chem. Eng. Progr. (1969) 65 (9), 47.
4. Berg, L., Chem. Eng. Progr. (1969) 65, (9), 53.
5. Tassios, Dimitrios, Chem. Eng. (Feb. 10, 1969) 76 (3), 118-22.
6. Bannister, R. R., Buck, E., Chem. Eng. Progr. (1969) 65 (9), 65.
7. Halflund, E. R., Chem. Eng. Progr. (1969) 65, 9.
1964.
9. Gerster, J. ., Chem. Eng. Progr. (1969) 65 (9), 43.
10. Black, C., Golding, R. ., Ditsler, D. E., Advan. Chem. Ser. (1972) 115, 64.
RECEIVED November 24, 1970.

2
Process Design Considerations for Extractive
Distillation: Separation of Propylene-Propane
ROMESH KUMAR, JOHN M. PRAUSNITZ, and C. JUDSON KING
Department of Chemical Engineering, University of California,
Berkeley, Calif. 94720
Extractive distillation is evaluated as an alternative to ordinary distillation for the separation of propylene-propane
mixtures. Varticular attention is given to the necessary compromises between different design factors: solvent concentration within the primary column, solvent selectivity, solvent
loss, etc. A major expense is associated with the sensible heat
requirements of the circulating solvent; process modifications
so as to minimize this expense are discussed. The process
analysis explores combinations of solvent selectivity and
other solvent properties which might make extractive distillation attractive. It appears that in almost all cases extractive distillation offers no advantage compared with ordinary
distillation. Only in special cases may circumstances warrant
extractive distillation. External factors favoring the use of
extractive distillation are identified.
' T p h i s w o r k explores the i m p o r t a n t v a r i a b l e s w h i c h m u s t be

* to d e s i g n a n e x t r a c t i v e d i s t i l l a t i o n process. T h e
the
e c o n o m i c effects o f these v a r i a b l e s a n d
S o m e of the
design variables may
s e p a r a t i o n cost w h i l e others m a y
considered
d i s c u s s i o n identifies
t h e i r p o s s i b l e interactions.
h a v e synergistic effects i n terms of

not.
A s a result, the
optimum design
for a n e c o n o m i c extractive d i s t i l l a t i o n process m u s t be a c o m p r o m i s e set

of values for the different process v a r i a b l e s . T h e s e c o m p r o m i s e s are
dis-
cussed and
pro-
are i l l u s t r a t e d for a p a r t i c u l a r casei.e., separation of
p a n e - p r o p y l e n e mixtures.
For
this c o m m e r c i a l l y i m p o r t a n t s e p a r a t i o n
f r a c t i o n a l d i s t i l l a t i o n is m o s t often u s e d , regardless of the
low
relative
v o l a t i l i t y ( a b o u t 1.13-1.19 at 200 p s i a ) .
E x t r a c t i v e d i s t i l l a t i o n is sometimes u s e d to
separate m i x t u r e s
w h i c h f r a c t i o n a l d i s t i l l a t i o n is difficult, s u c h as for
for
b i n a r y systems of
16

2.
K U M A R , PRAUSNITZ,
A N D
K I N G
Process Design
17
Considerations
c l o s e - b o i l i n g c o m p o n e n t s or for m u l t i c o m p o n e n t systems w h e r e t h e o r d e r
of c o m p o n e n t v o l a t i l i t i e s does n o t c o r r e s p o n d to the d e s i r e d d i s t r i b u t i o n
of c o m p o n e n t s b e t w e e n p r o d u c t s . I n extractive d i s t i l l a t i o n , a s e p a r a t i n g
agent, often c a l l e d the solvent, is a d d e d to t h e m i x t u r e to b e separated.
T h i s agent, or solvent, modifies the v o l a t i l i t y of e a c h c o m p o n e n t , one
different f r o m the other, b y its effects o n l i q u i d - p h a s e p r o p e r t i e s .
Such
effects c a n i n c l u d e f o r m i n g a s s o c i a t i o n complexes, a l t e r i n g e x i s t i n g assoc i a t i o n structures, etc. A s a result, the c o m p o n e n t r e l a t i v e v o l a t i l i t i e s i n

the presence of t h e solvent differ f r o m those i n t h e solvent-free m i x t u r e .
T h e f u n d a m e n t a l flow d i a g r a m for a n extractive d i s t i l l a t i o n process
is s h o w n i n F i g u r e 1. T h e f e e d enters the e x t r a c t i v e d i s t i l l a t i o n c o l u m n
( p r i m a r y c o l u m n ) i n w h i c h the solvent is a d d e d n e a r t h e t o p . T h e c o m p o n e n t ( o r c o m p o n e n t s ) w h o s e v o l a t i l i t y is the greatest i n t h e p r e s e n c e
of the solvent is d r i v e n o v e r h e a d i n this c o l u m n . T h e b o t t o m s consist of
the solvent a n d the o t h e r c o m p o n e n t
( o r c o m p o n e n t s ) ; these are f e d
to the solvent r e c o v e r y c o l u m n ( s e c o n d a r y c o l u m n ) .
The
regenerated
solvent is c o o l e d a n d f e d b a c k to t h e p r i m a r y c o l u m n .
I n m o s t cases, t h e solvent is m u c h less v o l a t i l e t h a n the f e e d c o m p o n e n t s ; i t is therefore present m a i n l y i n the l i q u i d p h a s e i n t h e p r i m a r y
column.
T h i s is d e s i r a b l e , as i t is the l i q u i d - p h a s e n o n i d e a l i t i e s w h i c h
g i v e r i s e to the greater s e p a r a t i o n factor b e t w e e n t h e f e e d c o m p o n e n t s .

H o w e v e r , there is a r e l a t i v e l y s m a l l a m o u n t of solvent i n t h e v a p o r phase,
a n d to a v o i d excessive loss of this solvent w i t h the t o p p r o d u c t i n t h e
p r i m a r y c o l u m n , sufficient trays are p r o v i d e d a b o v e t h e solvent a d d i t i o n
p l a t e to r e d u c e the solvent c o n c e n t r a t i o n i n the t o p p r o d u c t to a n acceptable level.
General
Considerations
F o r the process s h o w n i n F i g u r e 1, t h e m a i n u n i t s are t h e
two
distillation columns ( w i t h their reboilers a n d overhead condensers) a n d

the solvent cooler.
T h e major u t i l i t i e s are t h e heat r e q u i r e d i n t h e re-
boilers a n d the c o o l i n g duties of the condensers a n d t h e solvent cooler.

T h e d e s i g n o f the p r i m a r y c o l u m n d e p e n d s p r i m a r i l y o n t h e r e l a t i v e v o l a t i l i t y of t h e k e y c o m p o n e n t s ; i t is therefore s t r o n g l y d e p e n d e n t u p o n the
a c t i v i t y coefficients of these c o m p o n e n t s i n t h e solvent.
T h e v o l a t i l i t i e s of t h e f e e d c o m p o n e n t s r e l a t i v e to the solvent are
g e n e r a l l y h i g h ; therefore, the d e s i g n of the s e c o n d a r y c o l u m n is p r i m a r i l y
a f u n c t i o n of the solvent c i r c u l a t i o n rate. T h e c o n d e n s e r d u t i e s d e p e n d
o n the reflux ratios i n t h e t w o c o l u m n s w h i c h are thus affected b y the
r e l a t i v e v o l a t i l i t i e s . T h e solvent cooler d u t y is a f u n c t i o n of t h e solvent
c i r c u l a t i o n rate a n d t h e r e c o v e r y c o l u m n r e b o i l e r t e m p e r a t u r e w h i c h is
d e t e r m i n e d b y the solvent v o l a t i l i t y . T h e s u m of t h e r e b o i l e r d u t i e s i n

18
E X T R A C T I V E
Solvent
A N D
A Z E O T R O P I C
DISTILLATION
Propane
Product
Extractive Distillation
Column
Feed
Propylene
Solvent
Product
Recovery
Column
Steam
Solvent Cooler
Figure 1.
Extractive
distillation process flowsheet
t h e t w o c o l u m n s is a p p r o x i m a t e l y e q u a l to the s u m o f t h e heat r e m o v e d
i n the condensers a n d i n t h e solvent cooler.
The thermodynamic prop-
erties o f the solvent a n d the solvent r e c i r c u l a t i o n rate are o f major

i m p o r t a n c e i n the d e s i g n o f the extractive d i s t i l l a t i o n process.
Solvent Selection
Criteria
I m p o r t a n t solvent characteristics are selectivity, m i s c i b i l i t y w i t h t h e

feed, a n d v o l a t i l i t y .
Selectivity. T h e selectivity, S , is d e f i n e d as the r a t i o o f t h e a c t i v i t y
00
coefficients o f the k e y c o m p o n e n t s w h e n e a c h a l o n e i s present i n t h e

solvent at infinite d i l u t i o n . T h u s , for the p r o p a n e - p r o p y l e n e system
S =
y-osHe/yoeHe
(D
T h e a c t i v i t y coefficients o f the c o m p o n e n t s at other t h a n t r a c e c o n centrations i n the solvent d e p e n d o n the m i x t u r e c o m p o s i t i o n a n d , f o r

systems w i t h p o s i t i v e d e v i a t i o n f r o m R a o u l t ' s L a w , decrease t o w a r d u n i t y
as the c o m p o n e n t m o l e f r a c t i o n tends t o w a r d one. I n a s i m p l e , s y m m e t r i c

2.
K U M A R ,
19
Process Design Considerations
PRAUSNITZ, A N D K I N G
b i n a r y system, t h e l o g a r i t h m of the a c t i v i t y coefficient of t h e h y d r o c a r b o n

(A)
o r ( B ) is p r o p o r t i o n a l to t h e s q u a r e of the solvent m o l e f r a c t i o n ( I )
\ny
(lny> )x
A
l n y B = = (In
y )xs
B
E q u a t i o n 2, a l t h o u g h not h i g h l y a c c u r a t e for m a n y p r a c t i c a l systems,

was u s e d i n this w o r k as i t is c o n v e n i e n t to i m p l e m e n t a n d
provides a good
first-order
generally
approximation.
N e g l e c t i n g vapor-phase corrections a n d t h e P o y n t i n g effect, t h e r e l a

t i v e v o l a t i l i t y b e t w e e n the k e y c o m p o n e n t s i n the presence of t h e solvent is
"
A B
()
(PA)
(y )
(P%)
RT)
( 3 )
w h e r e P is the p u r e - c o m p o n e n t s a t u r a t i o n ( v a p o r ) pressure. E q u a t i o n 3
m a y b e w r i t t e n as
<*AB
(4)
-(ft)
S = y A/y
where
such t h a t
and
(x )
s
f (x )
f (x )
8
- 1
< 1
when x
for x
1
< 1
A h i g h selectivity gives a h i g h relative v o l a t i l i t y , m a k i n g a n easier

s e p a r a t i o n possible. S increases w i t h i n c r e a s i n g solvent c o n c e n t r a t i o n
(2),
b e c o m i n g a m a x i m u m at 1 0 0 % solvent, a n d u s u a l l y falls w i t h r i s i n g t e m p e r a t u r e . A n e x a m p l e is g i v e n i n F i g u r e 2, w h i c h shows the s e l e c t i v i t y

of t h e solvents f u r f u r a l a n d a c e t o n i t r i l e for p r o p a n e - p r o p y l e n e ,
m a t e d b y the p r o c e d u r e s of W e i m e r a n d P r a u s n i t z ( 3 ) .
as esti-
S is largest at
h i g h solvent concentrations a n d at l o w t e m p e r a t u r e s ; therefore, the separ a t i o n w o u l d b e easiest u n d e r these c o n d i t i o n s .

T h e search for a s u i t a b l e solvent for a p a r t i c u l a r s e p a r a t i o n w o u l d
b e greatly a i d e d i f the f e e d c o m p o n e n t
p r e d i c t e d f r o m t h e p u r e - c o m p o n e n t p r o p e r t i e s alone.
could
Tassios ( 2 )
be
de-
scribes a five-step p r o c e d u r e for e v a l u a t i n g solvents for extractive d i s t i l l a t i o n of h y d r o c a r b o n s . T w o of t h e m o r e u s e f u l correlations for p r e d i c t i n g

are those p r o p o s e d b y W e i m e r
a n d b y P i e r o t t i , D e a l , a n d D e r r (4).
and Prausnitz
(3)
T h e f o r m e r is u s e f u l w h e r e t h e f e e d
c o m p o n e n t s are s a t u r a t e d h y d r o c a r b o n s , olefins, or aromatics. F o r o t h e r

classes of h y d r o c a r b o n s , the latter is useful.
F o r a paraffin-olefin system o f the same n u m b e r of c a r b o n atoms i n
the absence of a solvent, the olefin is m o r e v o l a t i l e a n d is d r i v e n o v e r h e a d

20
E X T R A C T I V E
A N D
AZEOTROPIC
DISTILLATION
Temperature, C
Figure 2. Effect of temperature on solvent selectivity and
propane activity coefficient in furfural
and in acetonitrile
(calculated)
i n o r d i n a r y d i s t i l l a t i o n ; for p r o p a n e - p r o p y l e n e , /* is greater
t h a n u n i t y . A p o l a r solvent is u s e d i n extractive d i s t i l l a t i o n o f p a r a f f i n olefin m i x t u r e s s i n c e the olefin, because o f t h e l a r g e p o l a r i z a b i l i t y o f the
d o u b l e b o n d , forms a less n o n i d e a l system w i t h the solvent t h a n does t h e
paraffin.
I n these systems t h e paraffin a c t i v i t y coefficient is greater t h a n
t h a t of the olefin, t h e r e b y t e n d i n g to reverse the n a t u r a l r e l a t i v e v o l a t i l i t y

of t h e p a r a f f i n - o l e f i n s y s t e m ; f o r p r o p a n e - p r o p y l e n e , /7 8 is less
3
t h a n u n i t y . T o b e u s e f u l , a solvent m u s t reverse t h e r e l a t i v e v o l a t i l i t y to
s u c h a n extent t h a t (a e) w i t h solvent > ( j w i t h o u t solvent.
A
\<*AB
O n l y a few
e x p e r i m e n t a l investigations h a v e b e e n r e p o r t e d w h i c h
e v a l u a t e solvents for p a r a f f i n - o l e f i n separations.
Perhaps the most com-

2.
K U M A R ,
PRAUSNITZ,
A N D
Process Design
K I N G
21
Considerations
prehensive experimental data o n paraffin-olefin-solvent mixtures have

been reported b y Gerster, Gorton, a n d E k l u n d (5).
T h e s e authors r e p o r t
a c t i v i t y coefficient d a t a for n-pentane a n d 1-pentene i n b i n a r y systems

w i t h 33 different solvents at f o u r temperatures. T h e d a t a for n o n - h y d r o g e n
b o n d i n g solvents w e r e c o r r e l a t e d i n a p l o t o f selectivity vs. In yc5Hi2> **s
s h o w n i n F i g u r e 3. T h e c u r v e for h y d r o g e n b o n d i n g solvents falls l o w e r ;
i.e., t h e same 52 corresponds to a l o w e r selectivity. F i g u r e 3 shows
that f o r a p a i r o f h y d r o c a r b o n solutes c o n t a i n i n g t h e same n u m b e r o f
c a r b o n atoms, the a c t i v i t y coefficient o f one h y d r o c a r b o n i n b i n a r y s o l u
t i o n w i t h a p o l a r solvent is, t o a first a p p r o x i m a t i o n , a f u n c t i o n o f the
a c t i v i t y coefficient o f t h e o t h e r i n that solvent. A c t i v i t y coefficients
for
p r o p a n e - p r o p y l e n e , as e s t i m a t e d b y t h e m e t h o d of W e i m e r a n d P r a u s n i t z
( 3 ) , e x h i b i t b e h a v i o r s i m i l a r to t h a t n o t e d for a c t i v i t y coefficients o f the
n - p e n t a n e - l - p e n t e n e system w i t h i n the a c c u r a c y o f t h e e s t i m a t i o n p r o
cedure.
H o w e v e r , H a f s l u n d ( 6 ) has q u o t e d solvent selectivity d a t a for the
propane-propylene
system w h i c h d e v i a t e
c o n s i d e r a b l y f r o m the p l o t
g i v e n i n F i g u r e 3. S o m e o f these d a t a are also s h o w n i n that figure. I t

appears that a l t h o u g h most solvents m a y b e e x p e c t e d t o f a l l a l o n g the
2.2
X 2,2,3, Trichlorobutyronitrile
y
2.0
Butyronitrilt
Acrylonitrile y
X
y
1.8 -
y
Gerster' Plot
Bostd on Dota for
Ptfltant end Penttne
Acttone
1.6
1.4
^
'
S
Acetonitrilt
PrapiOMtril*
w i U M H 111 IB
X Dota Quoted by
HofthMd
X
Furfural
1.2
0MF
1
1 1 1 11 1 1
3 4 5 6 7 8 9
x
1.0
I
2
I l
15 20
I I I
30 40 50
Activity Coefficient of Propane, /
S 8
H
Figure 3.
Solvent selectivity as a function of activity coefficient of paraffin

in the solvent

22
E X T R A C T I V E
A N D
A Z E O T R O P I C
DISTILLATION
p l o t i n F i g u r e 3, there are s o m e solvents w h i c h s h o w s u b s t a n t i a l l y differ

ent selectivity. I n this w o r k , t w o sets o f c a l c u l a t i o n s w e r e m a d e for the
effect of s e l e c t i v i t y o n the process d e s i g n :
( 1 ) 7C3H v a r i e d w i t h S
8
00
a c c o r d i n g to t h e p l o t i n F i g u r e 3.
yc H8 w a s h e l d constant w i t h v a r y i n g values of S .
(2)
00
Miscibility with the Feed Components. I n a s o l u t e - s o l v e n t system

e x h i b i t i n g s t r o n g p o s i t i v e d e v i a t i o n s f r o m R a o u l t ' s L a w , the solute has
o n l y l i m i t e d s o l u b i l i t y i n the solvent. A b o v e a c e r t a i n solute c o n c e n t r a
t i o n , t w o l i q u i d phases a r e f o r m e d .
T h e p r e s e n c e of t w o l i q u i d phases
o n t h e plates o f a d i s t i l l a t i o n c o l u m n leads to i n s t a b i l i t y a n d o p e r a t i o n a l
p r o b l e m s . It is therefore necessary to ensure t h a t t h e solute c o n c e n t r a t i o n
i n the l i q u i d phase never exceeds its s o l u b i l i t y l i m i t . T h i s s o l u b i l i t y l i m i t
gives a m i n i m u m feasible solvent c o n c e n t r a t i o n i n t h e section b e l o w the
solvent a d d i t i o n p l a t e of the p r i m a r y c o l u m n .
A n a p p r o x i m a t i o n to the m i s c i b i l i t y l i m i t i n a b i n a r y system is o b
t a i n e d b y a s s u m i n g t h a t the p o l a r solvent is essentially i n s o l u b l e i n the
h y d r o c a r b o n . S i n c e the a c t i v i t y of the h y d r o c a r b o n i n t h e h y d r o c a r b o n
p h a s e is near u n i t y , at e q u i l i b r i u m i t m u s t b e the same as t h a t i n the
s o l v e n t - r i c h phase.
yx
A
Am
(5)
If w e f u r t h e r assume that E q u a t i o n 2 h o l d s for the b i n a r y system, w e h a v e
0=(1^)(1-^)
K n o w i n g In ^ , E q u a t i o n 6 y i e l d s x ,
00
Am
1^
(6)
t h e m o l e f r a c t i o n of A at the
l i m i t of its m i s c i b i l i t y i n t h e solvent.
Volatility.
F o r a fixed t o w e r pressure, the v o l a t i l i t y of the solvent
determines the reboiler temperature.
It also influences t h e n u m b e r of
e q u i l i b r i u m stages r e q u i r e d i n t h e solvent-recovery c o l u m n , as w e l l as
the n u m b e r of stages r e q u i r e d i n the solvent k n o c k - o u t section of t h e
p r i m a r y c o l u m n . F o r process e c o n o m i c s , t h e m o r e i m p o r t a n t o f
these
factors is g e n e r a l l y the t e m p e r a t u r e of t h e b o t t o m s f r o m t h e solventrecovery
c o l u m n since this is the highest solvent t e m p e r a t u r e i n the
process. T h e lowest solvent t e m p e r a t u r e is w h e r e t h e solvent is f e d i n t o

the p r i m a r y c o l u m n . T h e c h a n g e i n solvent t e m p e r a t u r e is p r o d u c e d b y
the solvent cooler, a n d t h e greater t h e t e m p e r a t u r e s w i n g b e t w e e n the
hottest a n d the coolest p o i n t s i n the solvent c i r c u i t , t h e h i g h e r is t h e heattransfer d u t y of the solvent cooler.
T h e s u m of the heat d u t i e s i n t h e reboilers is a p p r o x i m a t e l y e q u a l
to t h e s u m of the heat d u t i e s of the o v e r h e a d condensers a n d t h e solvent
cooler.
S i n c e the solvent v o l a t i l i t y influences the t e m p e r a t u r e l e v e l i n

2.
K U M A R ,
PRAUSNITZ, A N D KING
Process Design
23
Considerations
the reboilers, i t affects the heat i n p u t to t h e reboilers as w e l l as the heat

d u t y of the solvent cooler.
A s e c o n d a r y effect of t h e solvent v o l a t i l i t y is o n the o p e r a t i n g t e m p e r a t u r e of the extractive d i s t i l l a t i o n c o l u m n . A m o r e v o l a t i l e solvent
results i n a l o w e r average p l a t e t e m p e r a t u r e . A t the l o w e r t e m p e r a t u r e ,
the s e p a r a t i o n factor is g e n e r a l l y h i g h e r because of h i g h e r selectivity.
Table I.
Design Basis
Rate =
Composition =
Condition =
415 l b m o l e s / h r
50 mole % C H , 50 mole % C H ,
s a t u r a t e d v a p o r a t the tower
pressure"
Propylene
Purity =
Recovery =
Capacity =
99.0%
95.0%
75 m i l l i o n l b s / y r
Solvent
A m o u n t i n each h y d r o carbon product =

N o r m a l boiling point =
O t h e r p h y s i c a l properties =
C o n c e n t r a t i o n at s o l v e n t
feed p l a t e =
S
=
yC3H8 =
Feed
Coolant
Coolant =
Inlet temperature =
T e m p e r a t u r e rise i n
condensers =
M i n i m u m approach
temperature =
Cooler/Process
Heat
Exchangers
M i n i m u m approach
temperature =
^ 0 . 0 1 mole %
140F
those of acetone
0.85 to 0.90 mole f r a c t i o n
1.7 to 3.1
6.0 to 16.0
water
70 F
20F
10F
20F
" F o r binary distillation without solvent, the feed condition was taken as saturated liquid at the tower pressure.
Process Design
Process c a l c u l a t i o n s w e r e m a d e for t h e s e p a r a t i o n of a p r o p a n e - p r o p y l e n e m i x t u r e w i t h the d e s i g n basis s h o w n i n T a b l e I. F o r t h e present
c a l c u l a t i o n s , the solvent p h y s i c a l properties w e r e t a k e n as those of acetone.
T h e solvent s e l e c t i v i t y a n d the h y d r o c a r b o n a c t i v i t y coefficients
were
v a r i e d over the ranges g i v e n i n T a b l e I. A stage-to-stage ( L e w i s - M a t h e s o n ) m e t h o d ( 7 ) w a s u s e d to c a l c u l a t e the n u m b e r of e q u i l i b r i u m stages

r e q u i r e d i n the t w o towers, a l l o w i n g for v a r i a t i o n s i n
<X B
A
a n d interstage

24
E X T R A C T I V E
A N D
A Z E O T R O P I C
DISTILLATION
m o l a r flows f r o m stage to stage. T h e stage-to-stage, m a t e r i a l - a n d ent h a l p y - b a l a n c e p r o c e d u r e w a s also u s e d f o r the f r a c t i o n a l d i s t i l l a t i o n altern a t i v e , u s i n g t h e v a p o r - l i q u i d e q u i l i b r i u m d a t a of R e a m e r a n d Sage
(8)
for t h e p r o p a n e - p r o p y l e n e b i n a r y system.
T h e basis a n d v a r i o u s parameters f o r t h e e c o n o m i c analysis are g i v e n
i n T a b l e II. T h e o v e r a l l c o l u m n efficiency u s e d w a s o b t a i n e d f r o m a p l o t
of efficiency vs. the p r o d u c t of r e l a t i v e v o l a t i l i t y a n d l i q u i d v i s c o s i t y
c o r r e c t e d to m a t c h p r e d i c t e d (10)
(9),
d a t a for the p r o p a n e - p r o p y l e n e sys-
t e m . T h e v a l u e f r o m the p l o t ( 9 ) w a s i n c r e a s e d b y a factor r e q u i r e d to
m a k e the efficiency of t h e p r o p a n e - p r o p y l e n e b i n a r y d i s t i l l a t i o n e q u a l
to 1 0 0 % . Costs were calculated b y the Venture Analysis method
(11),
because this m e t h o d y i e l d s t h e a p p r o p r i a t e w e i g h t i n g factors for t h e
fixed
a n d o p e r a t i n g costs i n o r d e r to c a l c u l a t e t h e t o t a l costs. R e s u l t s a r e exp r e s s e d as a n n u a l costs, b e f o r e taxes.
T h e i m p o r t a n t process v a r i a b l e s
are discussed below.

Operating Temperature. T h e i m p o r t a n t temperatures for e c o n o m i c
analysis are the o v e r h e a d c o n d e n s e r temperatures at w h i c h heat is rem o v e d f r o m the process a n d t h e r e b o i l e r temperatures at w h i c h h e a t is
s u p p l i e d to t h e process. O f s i m i l a r i m p o r t a n c e is t h e t e m p e r a t u r e of t h e
s o l v e n t - a d d i t i o n p l a t e of t h e p r i m a r y c o l u m n s i n c e this t e m p e r a t u r e ,
together w i t h t h a t of the r e c o v e r y c o l u m n , establishes t h e t e m p e r a t u r e
s w i n g i n the solvent c i r c u i t .
O n e m e t h o d for
fixing
t h e v a r i o u s temperatures is to specify
the
o v e r h e a d c o n d e n s e r temperatures i n the t w o c o l u m n s . I n these c a l c u lations, it w a s d e c i d e d to use c o o l i n g w a t e r i n the t w o condensers, t h e r e b y

setting the reflux t e m p e r a t u r e at 100F for b o t h c o l u m n s . T h e c o n d e n s e r
t e m p e r a t u r e w o u l d n o r m a l l y b e set b y t h e a v a i l a b i l i t y of a n a d e q u a t e
heat sink, i f o t h e r t h a n w a t e r . F o r b i n a r y d i s t i l l a t i o n , t h e reflux t e m p e r a t u r e was also set at 100 F.
T h e c o n d e n s e r t e m p e r a t u r e of 100 F c o r r e s p o n d s to a pressure o f 187
p s i a i n the p r i m a r y c o l u m n a n d 222 p s i a i n the s e c o n d a r y t o w e r .
The
r e c o v e r y c o l u m n r e b o i l e r t e m p e r a t u r e t h e n comes to 495F, w h i l e the

extractive d i s t i l l a t i o n c o l u m n r e b o i l e r t e m p e r a t u r e varies f r o m a b o u t 300
to 425F.
T h e t e m p e r a t u r e of the s o l v e n t - a d d i t i o n p l a t e i n t h e m a i n
t o w e r v a r i e d f r o m 100 to 220F.
Solvent Loading.
T h e solvent c i r c u l a t i o n rate is a f u n c t i o n of the
reflux r a t i o i n t h e p r i m a r y t o w e r a n d the l i q u i d - p h a s e c o n c e n t r a t i o n of
the solvent. F o r a g i v e n solvent selectivity, as the solvent c o n c e n t r a t i o n
rises, the p r o p a n e - p r o p y l e n e relative v o l a t i l i t y increases a n d h e n c e the
r e q u i r e d reflux rate falls. T h e i n c r e a s e d r e l a t i v e v o l a t i l i t y results i n a
d e c r e a s e d n u m b e r of e q u i l i b r i u m stages r e q u i r e d f o r t h e d e s i r e d separat i o n . F i g u r e 4 shows t h e effect of solvent c o n c e n t r a t i o n o n the n u m b e r

2.
K U M A R ,
PRAUSNITZ,
A N D
Process Design
K I N G
Table II.
Considerations
25
Cost Calculation Basis
Materials =
a l l steel c o n s t r u c t i o n
T o w e r plates =
costs =
sieve t r a y s
Peters a n d T i m m e r h a u s {12),
H e a t exchangers =
costs =
floating-head,
% - i n c h tubes, 2 0 - f t - l o n g b u n d l e
Peters a n d T i m m e r h a u s , F i g u r e 1 4 - 1 5 , p. 566
F i g u r e 1 5 - 2 6 , p. 659
Utilities
H i g h pressure s t e a m (500 psig) =
$1.00/10
BTU
L o w pressure s t e a m
S0.40/10
BTU
(100 psig) =
Cooling water
$0.02/1000 g a l
Solvent =
$5 to 15/lb mole
T o w e r a n d heat exchanger s i z i n g procedures =

Venture Analysis
(11):
where
Peters a n d T i m m e r h a u s
V =
imlf -
R -
R =
S -
V =
S -
i
I
i
Iw
R
d
t
l
S
v e n t u r e profit
net profit
rate of r e t u r n on h i g h r i s k i n v e s t m e n t , 2 0 %
fixed c a p i t a l i n v e s t m e n t
average rate of r e t u r n on i n v e s t m e n t , 1 2 %
w o r k i n g c a p i t a l , 1 5 % of fixed c a p i t a l i n v e s t m e n t
gross profit
s t r a i g h t line d e p r e c i a t i o n factor, 0.1
corporate income t a x , 5 0 %
s i n k i n g f u n d d e p r e c i a t i o n rate, 0.05
sales revenue
m
f
=
=
=
=
=
=
=
=
=
=
=
C =
maintenance =
V =
(R -
Hw
dl,)t
- (S -
m a n u f a c t u r i n g cost, u t i l i t i e s +
6%
maintenance
of fixed c a p i t a l i n v e s t m e n t
0.5 S -
0.5 C +
0.22 J
therefore adjusted v e n t u r e cost
where
C
I
I
u
f
C +
=
=
=
cost of u t i l i t i e s
4.83 I (Peters a n d T i m m e r h a u s , T a b l e 17, p. 118)
p u r c h a s e d e q u i p m e n t cost
0.44
0.50 //
therefore the adjusted v e n t u r e cost, before taxes, is g i v e n b y
2.42

26
E X T R A C T I V E
0.84
0B6
0B8
A N D
A Z E O T R O P I C
DISTILLATION
0.90
Solvent Mole Fraction on Solvent Addition Plate, x
Figure 4. Effect of solvent concentration on the number of equilibrium stages and the solvent-to-feed ratio in primary
column
of stages r e q u i r e d a n d o n t h e s o l v e n t - t o - h y d r o c a r b o n feed r a t i o n e e d e d
f o r a solvent s e l e c t i v i t y S
= 1.7.
A rise i n solvent c o n c e n t r a t i o n decreases t h e reflux r a t i o i n t h e p r i m a r y c o l u m n , t h e r e b y l o w e r i n g the v a p o r flow rate i n t h e c o l u m n . C o n s e q u e n t l y , the t o w e r d i a m e t e r falls. A l s o , the i n c r e a s e d c o o l e r d u t y i s
a c c o m p a n i e d b y e n h a n c e d r e b o i l e r duties, r e s u l t i n g i n l a r g e r u t i l i t y costs.
W i t h rising solvent c o n c e n t r a t i o n , t h e m a i n t o w e r cost d e c l i n e s , b u t
the s o l v e n t - c o o l e r cost a n d the u t i l i t y cost increase. T h e net r e s u l t i s
s h o w n b y the s o l i d Unes i n F i g u r e 5 w h e r e the costs are r e p r e s e n t e d as
fixed, o p e r a t i n g , a n d t o t a l costs. A c o m p r o m i s e m u s t b e m a d e b e t w e e n the
t o w e r costs a n d the c o o l e r a n d u t i l i t y costs t o d e t e r m i n e the o p t i m u m
solvent c o n c e n t r a t i o n .

2.
A N D
Process Design
K I N G
Selectivity and A c t i v i t y Coefficients.
Considerations
27
T h e solvent s e l e c t i v i t y deter
m i n e s t h e r e l a t i v e v o l a t i l i t y o f t h e p r o p a n e - p r o p y l e n e system, w i t h a
higher selectivity y i e l d i n g a higher relative volatility of propane to pro
pylene.
A n i n c r e a s i n g s e l e c t i v i t y therefore
results i n a s m a l l e r reflux
r a t i o a n d f e w e r e q u i l i b r i u m stages r e q u i r e d for the s e p a r a t i o n . T h e l o w e r

reflux rate 'corresponds t o a l o w e r v a p o r - f l o w rate i n t h e t o w e r a n d h e n c e
to a t h i n n e r tower. T h e l o w e r reflux rate also results i n a s m a l l e r solventflow rate w i t h a c o n s e q u e n t decrease i n t h e s o l v e n t - c o o l e r size a n d d u t y
a n d i n the r e b o i l e r duties.
H o w e v e r , as s h o w n b y the p l o t i n F i g u r e 3 , t h e p r o p a n e a c t i v i t y
coefficient increases w i t h r i s i n g selectivity. T h e p r o p a n e a c t i v i t y coeffi
c i e n t p r i m a r i l y establishes the n u m b e r o f e q u i l i b r i u m stages i n the t o p
m o s t section o f t h e m a i n tower.
T h e h i g h e r the a c t i v i t y coefficient, t h e
h i g h e r t h e v a p o r - p h a s e c o n c e n t r a t i o n o f t h e solvent a n d c o n s e q u e n t l y
2600 -
Totol
2400
2200
2000
1800
Sf
1600
I
c
t
1400
1200
1000
800
tf-Total For
Fractional Distillation
Fixed
Without Heat Exchange System
With Heat Exchange System
600
400
_L
-L
0.84
0B6
0B8
0.90
Solvent Concentration, x
Figure 5.
Effect of solvent concentration
on annual costs

28
E X T R A C T I V E
A N D
A Z E O T R O P I C
DISTILLATION
t h e greater the n u m b e r o f stages a b o v e the solvent a d d i t i o n plate.
For
instance, w h e n yc3H8 = 6-0, six stages are r e q u i r e d i n t h e t o p m o s t sec

t i o n , whereas w h e n 8 = 1 6 0 , 24 stages are n e e d e d .
3
M o r e o v e r , re
verse f r a c t i o n a t i o n occurs i n t h e t o p m o s t section o f t h e m a i n c o l u m n

because, i n the absence o f the solvent, p r o p y l e n e is m o r e v o l a t i l e t h a n
p r o p a n e a n d therefore
tends t o g o o v e r h e a d .
T h e greater the n u m b e r
of stages i n the t o p section, the greater i s the extent o f this
reverse
f r a c t i o n a t i o n ; the r e c t i f y i n g section m u s t fractionate to a h i g h e r p r o p a n e

p u r i t y , a n d thus i t needs m o r e stages. A h i g h p r o p a n e a c t i v i t y coefficient
tends to increase the e q u i l i b r i u m stage r e q u i r e m e n t s .
C h a n g e s i n r e l a t i v e v o l a t i l i t y a n d a c t i v i t y coefficients w i t h c h a n g i n g
selectivity act against e a c h other i n affecting the e q u i l i b r i u m - s t a g e re
q u i r e m e n t s o f the m a i n c o l u m n . T h e net result i s s h o w n i n F i g u r e 6
w h e r e the t o t a l n u m b e r o f e q u i l i b r i u m stages i n the m a i n c o l u m n i s
Selectivity,
V e
Figure 6.
Variation of the number of equilibrium stages and solvent/

feed ratio in the primary column with selectivity

2.
A N D
K I N G
Process Design
29
Considerations
Without Heat Exchange System
Selectivity,
Figure 7.
Effect of solvent selectivity on annual costs
p l o t t e d against solvent selectivity. T h e effect of s e l e c t i v i t y o n the solventt o - h y d r o c a r b o n r a t i o is also s h o w n i n F i g u r e 6.

A h i g h e r s e l e c t i v i t y r e q u i r e s a t h i n n e r b u t t a l l e r tower.
I t also re
q u i r e s a s m a l l e r solvent cooler because o f t h e l o w e r solvent c i r c u l a t i o n

rate a n d s m a l l e r cooler a n d r e b o i l e r heat duties. T h e net r e s u l t is s h o w n
i n F i g u r e 7 w h e r e t h e s o l i d lines i n d i c a t e the a n n u a l costs as a f u n c t i o n
of selectivity; t h e y s h o w a f a l l i n g a n n u a l cost w i t h i n c r e a s i n g selectivity.
Process Modifications
F i g u r e s 5 a n d 7 s h o w that the o p e r a t i n g costs c o n s t i t u t e a large
f r a c t i o n o f the t o t a l a n n u a l cost o f the extractive d i s t i l l a t i o n process. I t is
therefore d e s i r a b l e to m o d i f y the b a s i c process to r e d u c e these costs.

30
E X T R A C T I V E
Solvent
A N D
A Z E O T R O P I C
DISTILLATION
Propane Product
Extractive
Distillation
Column
Feed
Solvent
Cooler
- 0
..Steam
-Main
Column
Reboiler
Bottoms
Preheater
Steam - - - - (
Extractive
Propylene
Product
Steam
Recovery Column
Reboiler
Waste Hef
Boiler
Figure 8.
E3
Solvent
Recovery
Column
distillation with heat recovery
O n e process m o d i f i c a t i o n is s h o w n i n F i g u r e 8. I n t h i s m o d i f i c a t i o n ,
a h e a t r e c o v e r y system uses the heat o f t h e r e c o v e r y c o l u m n b o t t o m s i n
t h e m a i n c o l u m n r e b o i l e r a n d i n a b o t t o m s preheater. I f a d d i t i o n a l heat
is n e e d e d i n the m a i n c o l u m n r e b o i l e r , a u x i l i a r y h e a t i n g i s p r o v i d e d as
s h o w n b y the ( d o t t e d ) steam c o i l i n F i g u r e 8. H o w e v e r , a waste heat
b o i l e r is sometimes n e e d e d ( s h o w n d o t t e d ) to r e m o v e the excess heat i n
t h e r e c o v e r y c o l u m n bottoms.
C o s t c a l c u l a t i o n s w e r e m a d e for this m o d i f i e d e x t r a c t i v e d i s t i l l a t i o n
process; t h e y are s h o w n b y the d a s h e d curves o n F i g u r e s 5 a n d 7. T h e
p r o p o s e d h e a t exchange system p r o v i d e s c o n s i d e r a b l e r e d u c t i o n i n the
a n n u a l costs of the extractive d i s t i l l a t i o n process. H o w e v e r , the extractive
d i s t i l l a t i o n costs are s t i l l greater t h a n those for a b i n a r y p r o p a n e - p r o p y l e n e
d i s t i l l a t i o n process as i n d i c a t e d o n F i g u r e s 5 a n d 7.
T h e d e s i g n c a l c u l a t i o n s d e s c r i b e d i n the p r e c e d i n g p a r a g r a p h s h a v e
b e e n m a d e u s i n g the f u n c t i o n a l r e l a t i o n b e t w e e n s e l e c t i v i t y a n d a c t i v i t y
coefficient f o u n d b y G e r s t e r et al. ( 5 ) .
H o w e v e r , the d a t a f r o m H a f s l u n d
( 6 ) , s h o w n i n F i g u r e 3, i n d i c a t e that this r e l a t i o n m a y not necessarily

2.
A N D
K I N G
Process Design
Considerations
31
h o l d f o r a l l solvents. T o i n v e s t i g a t e the effects o f i n c r e a s i n g s e l e c t i v i t y

w i t h o u t a c o r r e s p o n d i n g increase i n the p r o p a n e a c t i v i t y coefficient, p r o c
ess c a l c u l a t i o n s w e r e m a d e for v a r i o u s selectivities at a constant p r o p a n e
a c t i v i t y coefficient.
C o s t s w e r e c a l c u l a t e d for the process i l l u s t r a t e d i n
F i g u r e 8; t h e y are s h o w n i n F i g u r e 9. T h e costs decrease w i t h i n c r e a s i n g

selectivity, a n d the t o t a l extractive d i s t i l l a t i o n process cost i s a p p r o x i
m a t e l y the same as that for b i n a r y d i s t i l l a t i o n for p r o p a n e - p r o p y l e n e at
a selectivity of 2.6.
1100 r 1000
200 h
100-
I
2.0
I
I
I
2.4
2.8
Selectivity, /
3 8
C
3.2
3.4
.
3 6
H
Figure 9. Effect of solvent selectivity on annual costs at con

stant propane activity coefficient (process with heat exchange
system)
O t h e r process m o d i f i c a t i o n s m a y also b e i n v e s t i g a t e d . F o r e x a m p l e ,
F i g u r e 10 shows a n extractive d i s t i l l a t i o n process w i t h a n alternate m e t h o d
for solvent recovery.
H e r e , the m a i n c o l u m n b o t t o m s are flashed t o a
pressure l o w e n o u g h for the solvent to c o o l to the solvent-feed t e m p e r a

t u r e i n the m a i n c o l u m n . Besides d e c r e a s i n g the heat d u t y of the solvent

32
E X T R A C T I V E
E3
Solvent
A N D
A Z E O T R O P I C
DISTILLATION
Propane
Product
Extractive
Distillation
Column
Feed
Steam
1
r^C^^
>i ^ fFlosh \
H^T^
D r u m
Solvent
Recovery
Column
Propylene
Product
Steam
Solvent Cooler
Figure 10.
Extractive
distilhtion
with alternate solvent recovery
cooler, this m o d i f i c a t i o n also l o w e r s the a m o u n t o f f e e d t o t h e r e c o v e r y

c o l u m n a n d h e n c e leads t o a s m a l l e r s e c o n d a r y tower. H o w e v e r , s u c h a
m o d i f i c a t i o n r e q u i r e s v a p o r c o m p r e s s i o n o r r e f r i g e r a t i o n to p r o v i d e reflux
for t h e r e c o v e r y c o l u m n .
Conclusions
T h e costs o f s e p a r a t i n g p a r a f f i n - o l e f i n m i x t u r e s b y e x t r a c t i v e d i s t i l l a
t i o n are g r e a t l y affected b y t h e solvent selectivity, the paraffin a c t i v i t y
coefficient,
a n d t h e solvent v o l a t i l i t y ; t h e y d e p e n d
m o s t l y u p o n sol
v e n t characteristics. F o r a solvent t o b e effective t o separate k e y c o m

ponents A a n d B , t h e solvent m u s t h a v e a h i g h v a l u e o f yA/y w h i l e i t
m u s t also h a v e a l o w y A
F u r t h e r , t h e solvent v a p o r pressure s h o u l d b e
l o w e r , b u t n o t several orders o f m a g n i t u d e l o w e r , t h a n that o f the less

volatile hydrocarbon.
F o r the propanepropylenesolvent system, for the solvents e x h i b i t
i n g the functional relationship between S
00
a n d yc3H s h o w n i n F i g u r e 3,
8

2.
A N D
Process Design
K I N G
33
Considerations
i t does n o t seem l i k e l y t h a t extractive d i s t i l l a t i o n costs c a n b e r e d u c e d

b e l o w those of b i n a r y f r a c t i o n a l d i s t i l l a t i o n . F i g u r e 7 s h o w s d e c r e a s i n g
costs w i t h i n c r e a s i n g s e l e c t i v i t y b u t the slope of the c u r v e of cost vs. S
seems to be
flattening
out at S
0 0
0 0
of a b o u t 2, w h e r e e x t r a c t i v e d i s t i l l a t i o n
costs are s t i l l a b o u t 6 5 % greater t h a n t h e costs for b i n a r y d i s t i l l a t i o n .

H o w e v e r , for solvents w h i c h g i v e a h i g h selectivity at r e l a t i v e l y l o w e r
yC3H8> F i g u r e 9 shows a cost vs. S
c u r v e w h i c h i n d i c a t e s a l o w e r cost
for t h e extractive d i s t i l l a t i o n process at a solvent s e l e c t i v i t y h i g h e r t h a n

a b o u t 2.6.
It is e v i d e n t therefore t h a t the t h e r m o d y n a m i c characteristics ( S ,
00
38> S, yc H > etc. ) of the p r o p a n e - p r o p y l e n e - s o l v e n t system a r e m o s t

3
i m p o r t a n t i n d e t e r m i n i n g the e c o n o m i c s of extractive d i s t i l l a t i o n for this

separation. A c c u r a t e p r e d i c t i o n ( o r e x p e r i m e n t a l d e t e r m i n a t i o n ) of these
factors is essential for e c o n o m i c analysis of a n extractive d i s t i l l a t i o n
process.
H a f s l u n d (6)
reports that extractive d i s t i l l a t i o n has b e e n u s e d c o m
m e r c i a l l y i n one p a r t i c u l a r case to separate p r o p a n e - p r o p y l e n e . T h e f e e d

to the s e p a r a t i o n process w a s the off-gas f r o m a r e a c t o r i n a n e w process
for m a k i n g a c r y l o n i t r i l e a n d c o n s i s t e d of 40 w t % inerts, 39 w t %
C H ,
3
8 w t % C H , 7 w t % acrylonitrile, 5 w t % water, a n d 1 w t % by-product

3
i m p u r i t i e s . T h e p r o p y l e n e w a s to b e r e c o v e r e d for r e c y c l e to the reactor,

a n d the p r o p a n e a n d inerts w e r e to b e p u r g e d f r o m t h e system. A c r y l o
n i t r i l e w a s c h o s e n as the solvent for extractive d i s t i l l a t i o n . T h e t o p m o s t
section of the p r i m a r y c o l u m n w a s r e p l a c e d b y a w a t e r s c r u b b e r to r e c o v e r
t h e a c r y l o n i t r i l e i n the v e n t gas. T h e process r e p o r t e d b y H a f s l u n d ( 6 ) is
therefore s o m e w h a t different f r o m the processes i l l u s t r a t e d i n F i g u r e s
1, 8, a n d 10.
E x t r a c t i v e d i s t i l l a t i o n is c o m m e r c i a l l y u s e d for s e p a r a t i n g m i x t u r e s
of butanes, butnes, b u t a d i e n e s , a n d v a r i o u s acetylenes w i t h f o u r c a r b o n
atoms
(13).
S e p a r a t i n g these m u l t i c o m p o n e n t m i x t u r e s b y f r a c t i o n a l
d i s t i l l a t i o n is v e r y difficult b e c a u s e the n a t u r a l v o l a t i l i t i e s p f t h e v a r i o u s
c o m p o n e n t s , paraffinic as w e l l as olefinic, o v e r l a p c o n s i d e r a b l y . F o r i n stance, -butane is less v o l a t i l e t h a n 1-butene b u t m o r e v o l a t i l e t h a n cisa n d imrw-2-butenes. T h u s , s e p a r a t i o n of butanes f r o m butnes is m o r e
difficult b y f r a c t i o n a l d i s t i l l a t i o n t h a n b y extractive d i s t i l l a t i o n w h e r e the
solvent increases the v o l a t i l i t i e s of a l l the butanes to m a k e t h e m greater
t h a n the b u t e n e volatilities. F o r 1,3-butadiene r e c o v e r y extractive dist i l l a t i o n is also m o r e attractive t h a n o r d i n a r y d i s t i l l a t i o n b e c a u s e the large
p o l a r i z a b i l i t y of the c o n j u g a t e d d o u b l e b o n d s interacts s t r o n g l y w i t h t h e
p o l a r solvent. A l s o , i n C
h y d r o c a r b o n separations the solvent often o n l y
enhances a n d does not reverse the n a t u r a l r e l a t i v e v o l a t i l i t y for m a n y of

the c o m p o n e n t s ; h o w e v e r , e v e n for those c o m p o n e n t s for w h i c h the r e l a -

34
E X T R A C T I V E
A N D A Z E O T R O P I C
DISTILLATION
t i v e v o l a t i l i t y is r e v e r s e d b y the solvent, the solvent-free r e l a t i v e v o l a t i l i t y

is closer to u n i t y t h a n is that o f p r o p y l e n e to p r o p a n e i n the a b s e n c e of
solvent.
A l l these factors c o m b i n e to e x p l a i n w h y extractive d i s t i l l a t i o n
is r e l a t i v e l y m o r e attractive for C
h y d r o c a r b o n m i x t u r e s t h a n for C
hydrocarbon mixtures.
Acknowledgment
F o r financial s u p p o r t the authors are grateful to the N a t i o n a l S c i e n c e
F o u n d a t i o n . T h i s w o r k is b a s e d , i n part, o n a p r e v i o u s u n p u b l i s h e d s t u d y
b y . M . B a r r i s h ( U n i v e r s i t y of C a l i f o r n i a , B e r k e l e y , 1 9 6 4 ) .
Literature Cited
1. Prausnitz, J. M., "Molecular Thermodynamics of Fluid-Phase Equilibria,"
p. 193, Prentice-Hall, Englewood Cliffs, N. J., 1969.
2. Tassios, D., Chem. Eng. (1969) 76 (3), 118.
3. Weimer, R. F., Prausnitz, J. M., Hydrocarbon Process. Petrol. Refiner
(1965) 44 (9), 237.
4. Pierotti, G. T., Deal, C. H., Derr, E. L., Ind. Eng. Chem. (1959) 51, 95.
5. Gerster, J. ., Gorton, . ., Eklund, R-B., J. Chem. Eng. Data (1960) 5,
423.
6. Hafslund, E. R., Chem. Eng. Progr. (1969) 65 (9), 58.
7. King, C. J., "Separation Processes," Ch. 10, McGraw-Hill, New York, 1971.
8. Reamer, H. H., Sage, . H., Ind. Eng. Chem. (1951) 43, 1628.
9. Treybal, R. E., "Mass Transfer Operations," 2nd ed., p. 151, McGraw-Hill,
New York, 1968.
10. American Institute of Chemical Engineers, "Bubble-Tray Design Manual,"
p. 63, New York, 1958.
11. Rudd, D. F., Watson, C. C., "Strategy of Process Engineering," p. 80, Wiley,
New York, 1968.
12. Peters, M. S., Timmerhaus, K. D., "Plant Design and Economics for Chem
ical Engineers," 2nd ed., McGraw-Hill, New York, 1968.
13. Happel, J., Cornell, P. W., Eastman, DuB., Fowle, M. J., Porter, C. .,
Schutte, A. H., Trans. Amer. Inst. Chem. Eng. (1946) 42, 189.

3
Extractive Distillation by Salt Effect
WILLIAM F. FURTER
Department of Chemical Engineering, Royal Military College of Canada,
Kingston, Ontario
A salt dissolved in a mixed solvent is capable, through such
effects on the structure of the liquid phase as preferential
association and others, of altering the composition of the
equilibrium vapor. Hence salt effect on vapor-liquid equilibrium relationships provides a potential technique of
extractive distillation. A review is presented of the use of
dissolved salts, rather than liquid solvents, as separating
agents for extractive distillation.
V l T T h e n a salt is d i s s o l v e d i n a b o i l i n g s o l u t i o n o f t w o l i q u i d c o m ponents, there are s e v e r a l salt effects that m a y o c c u r . T h e s e i n c l u d e

a l t e r i n g o f the b o i l i n g p o i n t , the m u t u a l s o l u b i l i t i e s o f the t w o l i q u i d
c o m p o n e n t s i n e a c h other, a n d the c o m p o s i t i o n of the e q u i l i b r i u m v a p o r
phase.
T h i s p a p e r discusses the latter effect.
The
t e c h n i q u e o f u s i n g a salt rather t h a n a l i q u i d as a s e p a r a t i n g
agent for extractive d i s t i l l a t i o n is n o t n e w , b u t s u c h processes h a v e n o t

been w i d e l y used.
T h e t e c h n o l o g y has t e n d e d to b e p r o p r i e t a r y , a n d
the c h e m i s t r y i n v o l v e d has n o t b e e n w e l l u n d e r s t o o d . A l s o the systems

w h e r e a d i s s o l v e d s o l i d s e p a r a t i n g agent c a n b e a p p l i e d are l i m i t e d i n
n u m b e r b y s o l u b i l i t y restrictions. L i t e r a t u r e r e l a t i n g to this t e c h n i q u e a n d
its c h e m i s t r y has t e n d e d to b e f r a g m e n t a r y rather t h a n i n t e r r e l a t e d , a n d
m u c h o f i t has n o t b e e n w i d e l y c i r c u l a t e d . T h e r e is n o w g o o d e v i d e n c e
to s h o w that this t e c h n i q u e s h o u l d r e c e i v e m o r e attention.
F o r s u c h a process the
flowsheet
is b a s i c a l l y the same as that for a
n o r m a l extractive d i s t i l l a t i o n . T h e o n l y r e a l difference is that the separ a t i n g agent is a salt i n s t e a d o f a l i q u i d .
S i n c e a d i s s o l v e d salt is n o n -
v o l a t i l e , a l l of i t is c o n t a i n e d i n the l i q u i d phase, a n d a l l o f i t w i l l
flow
d o w n w a r d i n the c o l u m n . H e n c e , for i t to o c c u r t h r o u g h o u t the c o l u m n ,

it must b e f e d at o r near the top. T h e n o r m a l p l a c e is i n the r e e n t e r i n g
35
36
E X T R A C T I V E
EXTRACTIVE
DISTILLATION
COLUMN
REFLUX
AND
SALT
A N D
A Z E O T R O P I C
DISTILLATION
OVERHEAD
PRODUCT
DISSOLVER
SALT
RECYCLE
FEED
BOTTOMS
PRODUCT
Figure 1.
Flowsheet for extractive distillation

as the separating agent
using a dissolved
salt
reflux stream, as s h o w n i n F i g u r e 1. T h e salt, w h i c h m u s t b e soluble t o

some extent i n b o t h l i q u i d c o m p o n e n t s , is f e d b y d i s s o l v i n g i t at a steady
rate i n t o the h o t reflux just before r e e n t e r i n g the c o l u m n .
It is then
r e m o v e d f r o m the bottoms p r o d u c t for reuse, as is a l i q u i d s e p a r a t i n g

agent, b u t here i t is r e c o v e r e d b y e v a p o r a t i n g or d r y i n g i n s t e a d o f b y a
subsequent rectification step. T h e i n t r o d u c t i o n , use, recovery, a n d r e c y c l e
of the s e p a r a t i n g agent otherwise is the same for a d i s s o l v e d salt as i t is
for a l i q u i d solvent.
I n the simplest case the c h e m i c a l system i n v o l v e d w o u l d b e a f e e d
s o l u t i o n c o n s i s t i n g o f t w o v o l a t i l e components
(the
key
components),
w h i c h are t o b e separated f r o m e a c h other, a n d a n a d d e d

agent
(the
process.
third component),
separating
w h i c h circulates i n t e r n a l l y w i t h i n t h e
U s i n g the rectification o f e t h y l a l c o h o l - w a t e r
mixtures as a n
example, c u r r e n t i n d u s t r i a l processes use s e p a r a t i n g agents s u c h as b e n zene, toluene, o r 1-pentane i n a z e o t r o p i c d i s t i l l a t i o n or ethylene g l y c o l i n

e x t r a c t i v e d i s t i l l a t i o n . I n the t e c h n i q u e d e s c r i b e d here, one o f several
effective salts c a p a b l e o f e l i m i n a t i n g the e t h a n o l - w a t e r azeotrope, w o u l d
b e u s e d as the s e p a r a t i n g agent i n a n extractive d i s t i l l a t i o n to concentrate
e t h a n o l - w a t e r solutions to absolute a l c o h o l . A n e x a m p l e o f a p a r t i c u l a r l y

3.
F U R T E R
37
Salt Effect
effective salt w i t h this system is p o t a s s i u m acetate;
there are
several
others.
Besides u s i n g a single d i s s o l v e d salt as the s e p a r a t i n g agent,
there
are other w a y s a n d c o m b i n a t i o n s i n w h i c h salt is u s e d . F o r e x a m p l e , the

s e p a r a t i n g agent c o u l d consist of a m i x t u r e of t w o or m o r e salts, or one
or m o r e salts a d d e d to a l i q u i d s e p a r a t i n g agent to m a k e i t m o r e effective
a n d to r e d u c e the a m o u n t of the l i q u i d n e e d e d , o r one or m o r e salts
d i s s o l v e d i n a n i n e r t l i q u i d solvent w h i c h acts o n l y as a c a r r i e r for the
salt.
A l l possibilities h a v e
either b e e n u s e d or c o n s i d e r e d i n v a r i o u s
a p p l i c a t i o n s of this t e c h n i q u e .
H o w e v e r , o n l y the s i m p l e s t case, t h a t i n
w h i c h the s e p a r a t i n g agent consists o n l y of one c o m p o n e n t , a single salt,

is d i s c u s s e d here.
Advantages and
Disadvantages
W h y use a d i s s o l v e d salt i n s t e a d of a l i q u i d as a s e p a r a t i n g agent

for extractive d i s t i l l a t i o n ? F i r s t w e w i l l c o n s i d e r the disadvantages.
l i q u i d is s u p e r i o r to a s o l i d w h e n c o n s i d e r i n g ease of t r a n s p o r t a b o u t the
system, degree of s o l u b i l i t y i n the f e e d components, a n d rate of m i x i n g
at its feedpoint.
L i q u i d s m i x q u i c k l y , b u t a salt has to dissolve first. T h e r e
are also m e c h a n i c a l p r o b l e m s to b e o v e r c o m e i n m e t e r i n g a
finely-divided
s o l i d at a constant rate to a b o i l i n g or n e a r b o i l i n g l i q u i d m i x t u r e , a n d
i t m a y also b e difficult to a c h i e v e r a p i d d i s s o l v i n g of the salt after i t has
b e e n fed. B e c a u s e of s o l u b i l i t y l i m i t a t i o n s r e s t r i c t i n g the c h o i c e of a salt,
i t is also m o r e p r o b a b l e that a l i q u i d agent, r a t h e r t h a n a s o l i d , w h i c h is
effective a n d s o l u b l e w i l l exist for a g i v e n system.
H o w e v e r , i n the r e l a t i v e l y l i m i t e d n u m b e r of systems for w h i c h there
is a salt w h i c h is s o l u b l e a n d effective, some major advantages o v e r a
l i q u i d s e p a r a t i n g agent exist.
The
salt, b e i n g c o m p l e t e l y
nonvolatile,
exists o n l y i n t h e l i q u i d phase, a n d a l l of i t flows d o w n the c o l u m n a n d

o u t i n the bottoms p r o d u c t . A p r i n c i p a l a d v a n t a g e is that the o v e r h e a d
p r o d u c t , p r o v i d e d n o r m a l p r e c a u t i o n s are t a k e n against e n t r a i n m e n t , w i l l
b e c o m p l e t e l y free of s e p a r a t i n g agent. H e n c e there is n o n e e d for a n o t h e r
section of c o l u m n ( a solvent k n o c k b a c k section ) to b e l o c a t e d a b o v e the
f e e d p o i n t of the s e p a r a t i n g agent to s t r i p s e p a r a t i n g agent f r o m
o v e r h e a d p r o d u c t stream, as there is for a l i q u i d agent.
die
A l s o , less e n e r g y
is r e q u i r e d for the o p e r a t i o n since not e v e n p a r t of t h e s e p a r a t i n g agent is

v a p o r i z e d a n d c o n d e n s e d i n its c y c l e t h r o u g h the extractive d i s t i l l a t i o n
c o l u m n , as it w o u l d b e i f it w e r e a l i q u i d .
A n o t h e r p r i n c i p a l a d v a n t a g e is that the effect c a n b e large,
times m u c h larger t h a n is possible w i t h l i q u i d s e p a r a t i n g agents.
is because m u c h stronger forces
of association w i t h f e e d
someThis
component
m o l e c u l e s c a n b e exerted b y salt ions t h a n b y molecules o f a l i q u i d agent.

38
E X T R A C T I V E
A N D
A Z E O T R O P I C
DISTILLATION
T h e r e s u l t is t h a t m u c h less s e p a r a t i n g agent w o u l d n o r m a l l y b e n e e d e d ;
p e r h a p s o n l y a f e w p e r c e n t as c o m p a r e d w i t h the t y p i c a l 5 0 - 9 0 % o f the
l i q u i d p h a s e w h i c h is c o m m o n f o r s e p a r a t i n g agent c o n c e n t r a t i o n i n
extractive d i s t i l l a t i o n operations u s i n g l i q u i d t h i r d c o m p o n e n t s .
A re-
d u c e d r e q u i r e m e n t i n s e p a r a t i n g agent c o n c e n t r a t i o n a l l o w s savings t o
be made i n reduced c o l u m n diameter, reduced recovery
and recycle
c a p a c i t y for the s e p a r a t i n g agent, a n d r e d u c e d e n e r g y r e q u i r e d f o r the

r e c o v e r y a n d r e c y c l e step.
LIQUID COMPOSITION , MOLE % ETHANOL

Figure 2. Vapor-liquid
equilibrium data at atmospheric pressure for
the boiling ethanol-water system containing potassium acetate at saturation and at various constant
concentrations
T o i l l u s t r a t e h o w large the effect of a d i s s o l v e d salt c a n be, F i g u r e 2,
c a l c u l a t e d f r o m the d a t a o f M e r a n d a a n d F u r t e r ( J ) , i s i n c l u d e d t o
d e m o n s t r a t e b y h o w m u c h p o t a s s i u m acetate alters t h e v a p o r - l i q u i d e q u i l i b r i u m r e l a t i o n s h i p o f the system, b o i l i n g e t h a n o l - w a t e r at a t m o s p h e r i c
pressure. T h e d o t t e d c u r v e represents t h e e t h a n o l - w a t e r system alone,
w h e r e the azeotrope o c c u r s a t a b o u t 87 m o l e % e t h a n o l .
The
other
c u r v e s are for v a r i o u s concentrations o f p o t a s s i u m acetate, a n d a l l are

3.
F U R T E R
39
Salt Effect
c a l c u l a t e d o n a salt-free basis to p r o v i d e a c o m m o n basis f o r c o m p a r i s o n .

T h e upper curve, labelled # 5 i n the
figure,
acetate d i s s o l v e d i n the l i q u i d phase.
Its s a t u r a t i o n
its s o l u b i l i t y r a n g e s
from
49 mole
is for s a t u r a t e d p o t a s s i u m
concentrationi.e.,
% i n pure boiling water d o w n to
10 m o l e % i n p u r e b o i l i n g e t h a n o l , a n d i t increases r e l a t i v e
volatility
o v e r m u c h o f the r a n g e s h o w n b y a factor o f f o u r o r five times. T h e

i n t e r m e d i a t e curves, l a b e l l e d # 2 ,
3, a n d 4, are for salt concentrations
h e l d constant at 5, 10, a n d 20 m o l e % respectively.
E v e n small concen-
trations o f this p a r t i c u l a r salt c o m p l e t e l y e l i m i n a t e t h e azeotrope.

F i g u r e 3, t a k e n from t h e d a t a o f D o b r o s e r d o v
(2),
gives another
e x a m p l e of t h e s u b s t a n t i a l effect t h a t a salt, e v e n at r e a s o n a b l y
c o n c e n t r a t i o n , c a n h a v e i n c e r t a i n systems.
The
moderate
key components
are
a g a i n e t h a n o l a n d water, b u t h e r e t h e salt is c a l c i u m c h l o r i d e , present

at a constant c o n c e n t r a t i o n of 10 g r a m s / 1 0 0 m l of a l c o h o l - w a t e r s o l u t i o n .
T h e azeotrope has b e e n c o m p l e t e l y
eliminated, a n d relative
volatility
increased substantially.
LIQUID COMPOSITION , MOLE % ETHANOL

Figure 3. Vapor-liquid
the boiling ethanol-water
equilibrium
data at atmospheric pressure for
system containing calcium chloride at constant concentration

40
E X T R A C T I V E
A N D
A Z E O T R O P I C
DISTILLATION
A l t h o u g h most p r e v i o u s investigators of salt effect i n v a p o r - l i q u i d

e q u i l i b r i u m h a v e u s e d s a t u r a t e d r a t h e r t h a n constant salt concentrations
to measure the largest salt effect possible at e a c h v a l u e of l i q u i d c o m p o s i t i o n for a g i v e n salt i n a g i v e n system, this c o n d i t i o n is not representat i v e o f salt c o n c e n t r a t i o n i n a n extractive d i s t i l l a t i o n c o l u m n u s i n g diss o l v e d salt as t h e s e p a r a t i n g agent.
M o l a l salt c o n c e n t r a t i o n i n the l i q u i d
p h a s e w o u l d r e m a i n essentially constant f r o m t r a y to t r a y w i t h i n e a c h
of t h e r e c t i f y i n g a n d s t r i p p i n g sections just as constant as the a s s u m p t i o n
of constant m o l a l o v e r f l o w is v a l i d . F r o m a k n o w l e d g e of salt effect at
saturation, h o w e v e r , its effect at a constant c o n c e n t r a t i o n b e l o w s a t u r a t i o n
is c a l c u l a t e d u s i n g the. salt effect e q u a t i o n
{3,4).
Chemistry of the Salt Effect

I n extractive d i s t i l l a t i o n a n a d d e d s e p a r a t i n g agent c a n m o d i f y
the
v a p o r - l i q u i d e q u i l i b r i u m r e l a t i o n s h i p o f the c o m p o n e n t s to b e s e p a r a t e d
i f it c a n a c h i e v e selective
m o l e c u l a r association w i t h one of t h e
key
c o m p o n e n t s o v e r t h e other i n the l i q u i d phase. T h e m o l e c u l e s o f a l i q u i d

s e p a r a t i n g agent o r the ions of a salt t e n d to f o r m association c o m p l e x e s
m o r e w i t h the m o l e c u l e s of one of the f e e d c o m p o n e n t s to b e separated
t h a n w i t h t h e m o l e c u l e s of the other f e e d c o m p o n e n t .
It c a n alter the
v a l u e o f r e l a t i v e v o l a t i l i t y a n d the ease of s e p a r a t i o n of the system a n d

shift o r e v e n e l i m i n a t e a n a z e o t r o p e i f p r o p e r l y chosen. S i n c e the a d d e d
agent p r o b a b l y complexes to some extent w i t h b o t h k e y components, the
v o l a t i l i t i e s of b o t h w i l l m o s t l i k e l y t e n d to b e l o w e r e d , b u t b y differing
a m o u n t s d e p e n d i n g o n h o w selective the agent is i n its preference
c o m p l e x i n g w i t h one k e y c o m p o n e n t o v e r t h e other.
for
Since a separating
a g e n t for extractive d i s t i l l a t i o n n o r m a l l y is chosen so t h a t it prefers t h e less

v o l a t i l e of the f e e d c o m p o n e n t s , the v a l u e of r e l a t i v e v o l a t i l i t y is a c t u a l l y
i n c r e a s e d b y the agent e v e n t h o u g h t h e i n d i v i d u a l v o l a t i l i t i e s of b o t h
feed components may have been reduced i n value.
T h e earliest references
to the p h e n o m e n o n of a salt i n t h e l i q u i d
i n f l u e n c i n g v a p o r c o m p o s i t i o n go b a c k to the 1 3 t h c e n t u r y A D
chemists e x p e r i m e n t i n g w i t h the d i s t i l l a t i o n of a l c o h o l f r o m
when
fermented
m a s h r e c o r d e d t h a t t h e presence of p o t a s s i u m c a r b o n a t e i n the s t i l l p o t
e n r i c h e d t h e a l c o h o l content of the v a p o r ( 5 ) .
M o s t of the w o r k d o n e i n
the field o f salt effect i n d i s t i l l a t i o n is g r o u p e d i n t o three g e n e r a l categories:
salt effect
o n v a p o r - l i q u i d e q u i l i b r i u m , extractive
distillation
u s i n g d i s s o l v e d salts as s e p a r a t i n g agents, a n d s o l u t i o n theory of electrolytese.g., d i s s o l v e d s a l t s i n m i x e d solvents of t w o or m o r e components.

T h e first t w o categories h a v e t e n d e d to interest c h e m i c a l engineers a n d
chemists, w h i l e the t h i r d , g e n e r a l l y n e g l e c t i n g the effect o n v a p o r c o m -

3.
41
Salt Effect
F U R T E R
p o s i t i o n , has p r i m a r i l y interested p h y s i c a l chemists. A l l three categories,

h o w e v e r , are i n t e r r e l a t e d .
K a b l u k o v (6, 7, 8 )
i n 1891 a n d M i l l e r ( 9 )
i n 1897 o b s e r v e d
the
effects o f various salts, d i s s o l v e d i n t h e l i q u i d phase, o n the v a p o r - l i q u i d

e q u i l i b r i u m r e l a t i o n s h i p of t h e s y s t e m e t h a n o l - w a t e r .
M o s t of the salts
t h e y i n v e s t i g a t e d w e r e m o r e s o l u b l e i n w a t e r t h a n i n e t h a n o l , a n d these
w e r e o b s e r v e d t o e n r i c h the e q u i l i b r i u m v a p o r i n e t h a n o l . H o w e v e r ,
one
salt, m e r c u r i c c h l o r i d e , w h i c h is m o r e s o l u b l e i n e t h a n o l t h a n i n w a t e r ,
has the reverse effect.
B o t h investigators c o n c l u d e d t h a t a salt t e n d e d
to e n r i c h the v a p o r phase i n that c o m p o n e n t of the l i q u i d i n w h i c h i t w a s

less s o l u b l e . T h e y also o b s e r v e d t h a t the m a g n i t u d e of t h e selective effect
of a salti.e.,
the a m o u n t b y w h i c h i t alters v a p o r
r e l a t e d to the degree of difference
compositionis
i n its s o l u b i l i t i e s i n p u r e w a t e r a n d
p u r e a l c o h o l . M a g n i t u d e of salt effect is also a f u n c t i o n of t h e a m o u n t o f

salt present a n d is l i m i t e d b y the d e g r e e of s o l u b i l i t y of the salt i n the
l i q u i d phase. T h e s e b a s i c observations, m a d e o n this p a r t i c u l a r system,
h a v e t e n d e d to b e c o n f i r m e d as g e n e r a l i n other systems b y m o r e recent
investigators.
T h e most p o p u l a r system i n w h i c h the effects of v a r i o u s salts h a v e
b e e n i n v e s t i g a t e d o v e r the years has b e e n that of e t h a n o l - w a t e r .
Other
systems w h i c h h a v e b e e n s t u d i e d are e t h y l e n e g l y c o l - w a t e r , acetic a c i d water,
methanol-water,
acetone-methanol,
1-
and
2-propanol-water,
1-octane-propionic
nitric
acid, phenol-water,
acid-water,
and
formic
a c i d - w a t e r . A q u e o u s systems h a v e b e e n choices for s u c h studies b e c a u s e

of salt s o l u b i l i t y considerations.
L i t e r a t u r e p e r t a i n i n g to salt effect i n v a p o r - l i q u i d e q u i l i b r i u m a n d
to extractive d i s t i l l a t i o n u s i n g salt effect w a s r e c e n t l y r e v i e w e d b y F u r t e r
a n d C o o k ( 1 0 ) , a n d the t h e o r y a n d t e c h n i c a l aspects w e r e r e v i e w e d
F u r t e r (11).
by
V a p o r - l i q u i d e q u i l i b r i u m d a t a for 188 systems c o n t a i n i n g
salt w e r e p r e v i o u s l y c o m p i l e d b y C i p a r i s (12),
w h o has also p u b l i s h e d a
recent b o o k w i t h D o b r o s e r d o v a n d K o g a n o n t h e theory a n d p r a c t i c e of
extractive d i s t i l l a t i o n b y salt effect
(13).
T h e c h e m i s t r y r e l a t i n g to the use of d i s s o l v e d salts as s e p a r a t i n g

agents has not yet b e e n f u l l y u n d e r s t o o d . A p r i n c i p a l reason for this is
the c o m p l e x i t y o f effects that the salt c a n h a v e , a n d h o w these c a n v a r y
not o n l y f r o m system to system b u t , m o r e significantly, w i t h i n a g i v e n
system as the concentrations of a n y or a l l of the system c o m p o n e n t s are
varied.
F o r the a p p a r e n t l y s i m p l e system defined earlier, c o n s i s t i n g of
t w o v o l a t i l e c o m p o n e n t s p l u s a d i s s o l v e d salt, t h e salt c o u l d t h e o r e t i c a l l y
range f r o m f u l l y d i s s o c i a t e d into t w o types of ions to t o t a l l y associated.
If its d i s s o c i a t i o n is a n y w h e r e b e t w e e n these t w o extremes as i t p r o b a b l y
is, it exists as three species: t w o types of ions, p l u s u n d i s s o c i a t e d salt
molecules.
A l l three species c o n t r i b u t e t o the salt effect o n t h e ac-

42
E X T R A C T I V E
t i v i t y of
each volatile component,
A N D
A Z E O T R O P I C
DISTILLATION
a n d t h e i r parts are p r o b a b l y a l l
different b u t are i n t e r r e l a t e d . H e n c e , the effect of a salt e v e n i n a g i v e n

s y s t e m is a f u n c t i o n o f its d e g r e e of d i s s o c i a t i o n , w h i c h i n t u r n is a
f u n c t i o n o f l i q u i d p h a s e c o m p o s i t i o n , w h i c h varies f r o m p o i n t to p o i n t
w i t h i n the r e c t i f i c a t i o n c o l u m n .
T h e forces w h i c h cause association complexes w i t h i n the l i q u i d p h a s e
to f o r m m a y also differ f r o m system to system a n d f r o m salt to salt, a n d
c a n i n c l u d e , for e x a m p l e , forces s u c h as v a n d e r W a a l forces, electrostatic
i n t e r a c t i o n s of a t t r a c t i o n a n d r e p u l s i o n , h y d r o g e n b o n d i n g , o r c o m b i n a tions of s u c h forces.
T o c o m p l i c a t e matters m o r e , the association tendencies of salt ions
i n f o r m i n g association complexes w i t h m o l e c u l e s o f the f e e d c o m p o n e n t s ,
besides a l t e r i n g t h e i r v o l a t i l i t i e s , t e n d to r e d u c e t h e s o l u b i l i t y of
one
v o l a t i l e c o m p o n e n t i n the other. U s i n g the o l d m a x i m of p h y s i c a l c h e m i s t r y t h a t " l i k e dissolves l i k e , " t h e selective c o m p l e x i n g of t h e salt w i t h t h e

m o l e c u l e s of one v o l a t i l e c o m p o n e n t o v e r those of the other c a n
be
v i s u a l i z e d as m a k i n g the m o l e c u l e s of the t w o v o l a t i l e c o m p o n e n t s c h e m i c a l l y m o r e d i s s i m i l a r to e a c h other i n s o l u t i o n . T h e effect c a n b e so great

i n extreme cases that t w o l i q u i d phases c a n b e m a d e to f o r m e v e n i n
b o i l i n g solutions o f w h a t are n o r m a l l y h i g h l y m i s c i b l e l i q u i d s .
One
e x a m p l e o f a s y s t e m w h e r e this has b e e n o b s e r v e d is e t h a n o l - w a t e r c o n t a i n i n g a m m o n i u m sulfate d i s s o l v e d to s a t u r a t i o n .

T h e r e are o t h e r c o m p l i c a t i o n s . T h e salt, besides f o r m i n g association
complexes
w i t h s o l u t i o n m o l e c u l e s , p o s s i b l y c o u l d also alter or
even
destroy a l r e a d y - e x i s t i n g self-interactions of the m o l e c u l e s of a v o l a t i l e

c o m p o n e n t e i t h e r w i t h themselves or w i t h those o f the other f e e d c o m ponent. A n e x a m p l e is the associated s t r u c t u r e i n w h i c h l i q u i d w a t e r a n d
to a lesser extent s o m e alcohols exist. T h e effects of salt ions o n w a t e r w a t e r , w a t e r - a l c o h o l , a n d a l c o h o l - a l c o h o l c o m p l e x i n g , for e x a m p l e , m u s t
b e p r o f o u n d at h i g h e r salt concentrations, a n d w i l l v a r y i n a g i v e n system
w i t h salt c o n c e n t r a t i o n a n d w i t h a l c o h o l - w a t e r p r o p o r t i o n a l i t y i n t h e
l i q u i d . A l s o , associations of several, r a t h e r t h a n just p a i r s , of l i q u i d - p h a s e
species m a y f o r m .
T h e f u l l c o m p l e x i t y of w h a t i n i t i a l l y seems to b e a
r a t h e r s i m p l e s y s t e m finally becomes e v i d e n t w h e n i t is c o n s i d e r e d that t h e

s u m of i n d i v i d u a l effects w h i c h m a k e u p the o v e r a l l effect of t h e salt o n
t h e c o m p o s i t i o n o f the e q u i l i b r i u m v a p o r e v e n i n a g i v e n system are f u n c tions o f t h e r e l a t i v e p r o p o r t i o n s of a l l c o m p o n e n t s present a n d v a r y w i t h
l i q u i d p h a s e c o m p o s i t i o n o v e r the entire r a n g e i n v o l v e d i n t h e s e p a r a t i o n .
V a r i o u s theories h a v e b e e n p r o p o s e d a n d tested to e x p l a i n salt effect
i n v a p o r - l i q u i d e q u i h b r i u m , i n c l u d i n g models based o n hydration, intern a l pressure, electrostatic i n t e r a c t i o n , a n d v a n d e r W a a l forces. A l t h o u g h
the electrostatic t h e o r y o f D e b y e as m o d i f i e d for m i x e d solvents has h a d
l i m i t e d success, n o s i n g l e t h e o r y has y e t b e e n a b l e to a c c o u n t for or to

3.
43
Salt Effect
F U R T E R
p r e d i c t salt effect o n v a p o r - l i q u i d e q u i l i b r i u m f r o m
pure-component
p r o p e r t i e s alone. P r e v i o u s investigators h a v e g e n e r a l l y a g r e e d that s u c h

effects are c a u s e d b y a c o m p l e x i t y of forces a n d i n t e r a c t i o n s , n o o n e of
w h i c h has b e e n f o u n d significant e n o u g h i n r e l a t i o n to a l l of the others
to correlate w e l l other t h a n i n extremely l i m i t e d c i r c u m s t a n c e s .
Nevertheless, this a b i l i t y of a salt, w h i c h is not present i n the v a p o r
phase, to alter v a p o r
c o m p o s i t i o n , has n o t w h o l l y e s c a p e d
industrial
a t t e n t i o n a l t h o u g h its a p p l i c a t i o n s h a v e b e e n r e l a t i v e l y l i m i t e d .
Some Applications
D o n a l d F . O t h m e r w h i l e at E a s t m a n K o d a k d u r i n g the 1920's e x p e r i m e n t e d u s i n g salts to concentrate a c e t i c a c i d ( 1 4 ) .
H e also d e v e l o p e d a n
i n d u s t r i a l process for d i s t i l l i n g acetone f r o m its a z e o t r o p e w i t h m e t h a n o l

b y p a s s i n g a c o n c e n t r a t e d c a l c i u m c h l o r i d e b r i n e d o w n t h e rectification
column (J5).
P u r e acetone w a s c o n d e n s e d o v e r h e a d , a n d acetone-free
m e t h a n o l was r e c o v e r e d i n a separate s t i l l f r o m the b r i n e w h i c h w a s t h e n

recycled.
T h e i m p r o v e d O t h m e r r e c i r c u l a t i o n s t i l l (16)
has b e e n
the
a p p a r a t u s g e n e r a l l y f a v o r e d b y investigators w h o h a v e s t u d i e d the effects

of salts o n v a p o r - l i q u i d e q u i l i b r i u m .
C o o k a n d F u r t e r (17, 18)
r e p o r t e d the results of a s e m i w o r k s s t u d y
i n w h i c h aqueous e t h a n o l feedstocks w e r e f r a c t i o n a t e d i n a 12-tray b u b b l e

c a p c o l u m n i n a n extractive d i s t i l l a t i o n u s i n g p o t a s s i u m acetate as t h e
s e p a r a t i n g agent. A m e t h o d w a s d e v e l o p e d i n w h i c h the salt w a s f e d as
a g r a n u l a r s o l i d b y p o s i t i v e - d i s p l a c e m e n t m e t e r i n g s c r e w to the h o t reflux,
a l l o w i n g salt to b e f e d successfully at a steady rate w i t h o u t
backflow
o r loss of v a p o r a n d a v o i d i n g a n y c l o g g i n g o f salt b y c o n d e n s e d
d u r i n g feeding.
R a p i d d i s s o l v i n g of the salt i n the reflux w a s
vapor
achieved
b y e s t a b l i s h i n g a fluidized b e d of d i s s o l v i n g salt at the salt feedpoint.

e n t r a i n m e n t of salt i n t o t h e o v e r h e a d
product was encountered.
No
The
a z e o t r o p e was e l i m i n a t e d c o m p l e t e l y b y as l i t t l e as 5 m o l e % salt present

i n the l i q u i d phase, a l l o w i n g 9 9 . 9 % +
anhydrous alcohol,
completely
salt-free, to b e p r o d u c e d f r o m e v e n r e l a t i v e l y d i l u t e feedstocks
i n the
12-tray c o l u m n . T h e l o w salt c o n c e n t r a t i o n r e q u i r e d is i n s t r i k i n g c o n trast to the 1:1 to 4:1 r a n g e of t y p i c a l s o l v e n t - f e e d r a t i o r e q u i r e d for this

system u s i n g l i q u i d s e p a r a t i n g agents e v e n w i t h h i g h l y
concentrated
e t h a n o l feedstocks.
F o r m a n y years D E G U S S A i n G e r m a n y l i c e n s e d a t e c h n i q u e k n o w n
as the H I A G process (19, 20)
for d i s t i l l i n g absolute e t h a n o l , u s i n g m i x e d
acetate salts as the s e p a r a t i n g agent, i n the days w h e n e t h a n o l w a s u s e d

as a f u e l u p g r a d i n g a d d i t i v e i n a u t o m o t i v e gasolines p r o d u c e d i n c e r t a i n

44
E X T R A C T I V E
A N D
A Z E O T R O P I C
DISTILLATION
countries. O v e r 100 s u c h p l a n t s w e r e b u i l t b e t w e e n 1930 a n d 1950. U s e r s

c l a i m e d l o w e r c a p i t a l costs a n d l o w e r e n e r g y r e q u i r e m e n t s i n c o m p a r i s o n
w i t h c o n v e n t i o n a l processes w h i c h use b e n z e n e o r e t h y l e n e g l y c o l as the
s e p a r a t i n g agent, a n d the 9 9 . 8 % e t h a n o l p r o d u c e d r e q u i r e d n o f u r t h e r
p u r i f y i n g or solvent k n o c k b a c k to r i d i t of traces of s e p a r a t i n g agent.
A n e x a m p l e of a c o m m e r c i a l extractive d i s t i l l a t i o n o p e r a t i o n i n c u r r e n t major use u s i n g a salt is t h e c o n c e n t r a t i o n of aqueous n i t r i c a c i d u s i n g
m a g n e s i u m n i t r a t e as t h e s e p a r a t i n g agent i n s t e a d of t h e earlier process
which
h a d used a l i q u i d separating
agent,
sulfuric acid.
developers of this process h a v e b e e n H e r c u l e s a n d Tennessee
Principal
Eastman
i n the U n i t e d States a n d I m p e r i a l C h e m i c a l I n d u s t r i e s i n B r i t a i n .
Her-
cules, w h i c h i n s t a l l e d the process at P a r l i n , N . J . , 13 years ago, c l a i m s

s e v e r a l s t r o n g advantages
for u s i n g m a g n e s i u m n i t r a t e , a salt, as the
s e p a r a t i n g agent i n s t e a d of s u l f u r i c a c i d (21).
T h e y report
operating
costs r e d u c e d b y h a l f l a r g e l y t h r o u g h savings i n r e d u c e d e n e r g y r e q u i r e ments, c a p i t a l costs r e d u c e d 3 0 to 4 0 % , a h i g h e r y i e l d of p r o d u c t at

h i g h e r q u a l i t y , a n d less p o l l u t i o n of the atmosphere.
O t h e r i n d u s t r i a l a p p l i c a t i o n s h a v e existed, a n d these are
elsewhere
reviewed
(10).
Conclusions
E x t r a c t i v e d i s t i l l a t i o n u s i n g a d i s s o l v e d salt i n p l a c e of a l i q u i d
solvent as t h e s e p a r a t i n g agent is a n u n u s u a l u n i t o p e r a t i o n for a p p l i c a t i o n i n c e r t a i n specific systems w h e r e r e l a t i v e l y s m a l l concentrations of
salt are c a p a b l e of a l t e r i n g c o n s i d e r a b l y t h e v a p o r - l i q u i d e q u i l i b r i u m r e l a t i o n s h i p . T h e systems to w h i c h the t e c h n i q u e is a p p l i c a b l e are r e l a t i v e l y
l i m i t e d i n n u m b e r b y the a v a i l a b i l i t y of a n effective salt f o r a g i v e n system
w h i c h is a d e q u a t e l y s o l u b l e i n t h e system o v e r the c o m p o s i t i o n r a n g e i n v o l v e d a n d is selective. W h e r e a p p l i c a b l e , h o w e v e r , the effect c a n sometimes b e v e r y large a n d as a result c a n g r e a t l y r e d u c e t h e a m o u n t of
s e p a r a t i n g agent r e q u i r e d , a l o n g w i t h y i e l d i n g a n o v e r h e a d p r o d u c t c o m p l e t e l y free of s e p a r a t i n g agent d i r e c t l y f r o m the t o p of t h e c o l u m n
without the requirement
for a k n o c k b a c k section.
T h i s t e c h n i q u e is
d e s e r v i n g of m o r e a t t e n t i o n t h a n the relative o b s c u r i t y to w h i c h i t has

b e e n r e l e g a t e d to date.
Acknowledgment
T h e c o n t i n u e d r e s e a r c h p r o g r a m s o n extractive d i s t i l l a t i o n b y salt
effect a n d o n salt effect i n v a p o r - l i q u i d e q u i h ' b r i u m at t h e R o y a l M i l i t a r y
C o l l e g e of C a n a d a are s u p p o r t e d b y t h e D e f e n c e
R e s e a r c h B o a r d of
C a n a d a , G r a n t N o . 9530-40.

3.
FURTER
Salt Effect
45
Literature Cited
1. Meranda, D., Furter, W. F., Can.J.Chem. Eng. (1966) 44, 298.
2. Dobroserdov, L. L., Il'yina, V. P., Tr. Leningradskogo Tekhnol. Inst. Pish
chevoi Prom. (1956) 13, 92.
3. Johnson, A. I., Furter, W. F., Can. J. Chem. Eng. (1960) 38, 78.
4. Meranda, D., Furter, W. F., A.I.Ch.E. J. (1971) 17, 38.
5. Lescoeur, H., Ann. Chim. Phys. (1896) 9 (7), 541.
6. Kablukov, I. ., Zh. Russk. Fiz.-Khim. Obshch. (1891) 23, 388.
7. Kablukov, I. ., ibid (1903) 35, 548.
8. Kablukov, I. ., ibid (1904) 36, 573.
9. Miller, W. L., J. Phys. Chem. (1897) 1, 633.
10. Furter, W. F., Cook, R. ., Intern. J. Heat Mass Transfer (1967) 10, 23.
11. Furter, W. F., Chem. Engr. (London) (1968) 219, CE 173.
12. Ciparis, J. N., "Data of Salt Effect in Vapour-Liquid Equilibrium," Lith
uanian Agricultural Academy, Kaunas, Lithuania, USSR (1966).
13. Ciparis, J. N., Dobroserdov, L. L., Kogan, V. B., "Salt Rectification,"
Khimiya, Leningrad (1969).
14. Othmer, D. F., personal communication (April, 1969).
15. Othmer, D. F., personal communication to J. P. Hartnett (March 7, 1966).
16. Othmer, D. F., Anal. Chem. (1948) 20, 763.
17. Cook, R. ., Furter, W. F., "Extractive Distillation Employing a Dissolved
Salt as Separating Agent," A.I.Ch.E. 63rd National Meeting, St. Louis
(Feb. 18-21, 1968).
18. Cook, R. ., Furter, W. F., Can. J. Chem. Eng. (1968) 46, 119.
19. Intern. Sugar J. (1933) 35, 266.
20. "Herstellung von absolutem Alkohol nach dem HIAG-VERFAHREN DER
DEGUSSA," Degussa, Deusche Gold-und-Silber-Scheideanstalt, Vormals
Roessler, Frankfurt (Main), Germany.
21. Chem. Eng. News (June 9, 1958), 40.

4
Rapid Screening of Extractive Distillation
Solvents
Predictive and Experimental Techniques
Newark College of Engineering, Newark, N. J. 07102
Rapid predictive and experimental techniques for screening extractive distillation solvents are reviewed. In pre
paring a list of potential solvents the method of Scheibel
is recommended for non-hydrocarbon systems; for hydro
carbon systems solvents of high polar cohesive density
should be considered. For screening the potential sol
vents the method of Pierotti, Deal, and Derr is recom
mended. If it is not applicable, the method of Helpinstill
and Van Winkle should be considered next. Finally, re
liable screening is accomplished through a simple, rapid
technique recently developed that uses gas-liquid chro
matography.
" E x t r a c t i v e a n d a z e o t r o p i c d i s t i l l a t i o n i n different types o f c h e m i c a l

i n d u s t r y has b e c o m e m o r e i m p o r t a n t as m o r e separations of c l o s e - b o i l
i n g m i x t u r e s a n d a z e o t r o p i c ones are e n c o u n t e r e d . E x t r a c t i v e d i s t i l l a t i o n
is u s e d m o r e because i t is g e n e r a l l y less expensive, s i m p l e r , a n d c a n use
m o r e solvents t h a n a z e o t r o p i c d i s t i l l a t i o n . S o l v e n t s e l e c t i o n for a z e o t r o p i c
d i s t i l l a t i o n has r e c e n t l y b e e n d i s c u s s e d b y B e r g ( I ) .
T h e r e f o r e , solvent
s c r e e n i n g for extractive d i s t i l l a t i o n is d i s c u s s e d here.

T h e ease of s e p a r a t i o n o f a g i v e n m i x t u r e w i t h k e y c o m p o n e n t s i
a n d / is g i v e n b y the r e l a t i v e v o l a t i l i t y :
w h e r e is the l i q u i d phase m o l e fraction, y is the v a p o r p h a s e m o l e

f r a c t i o n , y is the a c t i v i t y coefficient, a n d P is the p u r e c o m p o n e n t v a p o r
pressure.
46
Library
American Chemical Society
4.
Extractive
TASSIOS
Distilfotion
47
Solvents
T h e solvent is i n t r o d u c e d t o c h a n g e t h e r e l a t i v e v o l a t i l i t y ( # ) as far
a w a y f r o m one as possible. S i n c e the r a t i o
(Pi/P )
is constant for s m a l l
t e m p e r a t u r e changes, t h e o n l y w a y t h a t t h e r e l a t i v e v o l a t i l i t y i s affected
is b y i n t r o d u c i n g a solvent w h i c h changes the r a t i o
(yi/,).
This ratio, i n
the presence o f the solvent, is c a l l e d selectivity (S^) :

Sii
[yi/r;] solvent
(2)
I n some cases a significant c h a n g e i n o p e r a t i n g pressure, a n d h e n c e

t e m p e r a t u r e , changes
e n o u g h t o e l i m i n a t e a n azeotrope ( 2 ) .
Besides a l t e r i n g t h e r e l a t i v e v o l a t i l i t y , t h e solvent s h o u l d also b e

easily s e p a r a t e d
from
the distillation products.
Other
criteriae.g.,
toxicity, cost, e t c . d i s c u s s e d b y V a n W i n k l e ( 2 ) a n d others m u s t b e

c o n s i d e r e d . R e l a t i v e v o l a t i l i t y e n h a n c e m e n t is d i s c u s s e d i n this p a p e r .
S e l e c t i n g the p r o p e r solvent b y c o n s i d e r i n g this c r i t e r i o n is s t i l l b a s e d
o n e m p i r i c a l a p p r o a c h e s because o f t h e large n o n i d e a l i t y o f the r e s u l t i n g
mixtures.
However,
g e n e r a l selection patterns a n d r a p i d e x p e r i m e n t a l
techniques have been made

presents a r e v i e w
a v a i l a b l e t h r o u g h t h e years.
o f some o f these m e t h o d s
This
paper
t o f a c i l i t a t e t h e solvent
selection process i n t h e c h e m i c a l i n d u s t r y . Q u a l i t a t i v e aspects a r e first

considered, followed
b y e m p i r i c a l correlations a n d r a p i d e x p e r i m e n t a l
techniques.
Qualitative
Considerations
Since the type
o f solutions e n c o u n t e r e d
i n extractive d i s t i l l a t i o n
i n v o l v e m i x t u r e s o f p o l a r c o m p o u n d s o r p o l a r w i t h n o n p o l a r ones, t h e
solutions a r e u s u a l l y n o n i d e a l , a n d p r e d i c t i n g t h e phase e q u i l i b r i u m
f r o m p u r e c o m p o n e n t d a t a o n l y is p r a c t i c a l l y i m p o s s i b l e . T h e o r e t i c a l a n d
e x p e r i m e n t a l studies t h r o u g h the years, h o w e v e r , h a v e e s t a b l i s h e d c e r t a i n
trends w h i c h are u s e d to s e a r c h f o r a n d screen p o t e n t i a l solvents.
Non-Hydrocarbon Mixtures: The Scheibel Method. S c h e i b e l ( 3 ) has
suggested that the p r o p e r solvent c a n b e f o u n d a m o n g t h e m e m b e r s o f
the h o m o l o g o u s series o f either k e y c o m p o n e n t s , i o r /
close t o o n e ) .
A n e x a m p l e p r e s e n t e d b y S c h e i b e l . ( 3 ) best demonstrates this a p p r o a c h .

C o n s i d e r i n g the separation o f the m e t h a n o l - a c e t o n e azeotrope, t h e p o t e n
t i a l solvents a c c o r d i n g t o this m e t h o d a r e presented i n T a b l e I. A n y
m e m b e r o f either h o m o l o g o u s series c a n b e u s e d . T h e reason b e h i n d this
a p p r o a c h is that w h i l e the m e m b e r s o f a h o m o l o g o u s series f o r m essen
t i a l l y i d e a l solutions, t h e y f o r m n o n i d e a l solutions w i t h t h e other c o m
ponent.
with
F o r e x a m p l e w h i l e m e t h a n o l forms essentially i d e a l solutions
ethanol,
1-propanol,
a n d 1-butanol,
n o n i d e a l solutions w i t h t h e m .
acetone
forms
increasingly
W h i l e t h e p a r t i a l pressure o f m e t h a n o l
decreases i n t h e presence o f a h i g h e r a l c o h o l , that o f acetone increases.

48
E X T R A C T I V E
Table I.
A N D
A Z E O T R O P I C
Potential Solvents for the Acetone "-Methanol
B.P.,
Solvent
Methylethyl
ketone
102.0
M e t h y l i s o b u t y l ketone
M e t h y l n - a m y l ketone,
etc.
Separation
B.P.,
Solvent
79.6
M e t h y l -propyl ketone
DISTILLATION
Ethanol
78.4
Propanol
97.8
115.9
Water
100.0
150.6
Butanol
A m y l alcohol
117.0
Ethylene
197.4
137.8
glycol
"Boiling point: 54.6C.

B o i l i n g point: 64.7C.
b
So that a n a z e o t r o p e w i t h acetone does not f o r m , the a l c o h o l u s e d m u s t

h a v e a h i g h e n o u g h b o i l i n g point.
T h i s r e q u i r e m e n t is r e l i a b l y
l i s h e d o n l y i f v a p o r - l i q u i d e q u i l i b r i u m d a t a for at least two,
estab
preferably
three, of the m e m b e r s of the series w i t h acetone are k n o w n . T h e P i e r o t t i Deal-Derr
method
(4)
( d i s c u s s e d l a t e r ) o r the T a s s i o s - V a n
Winkle
m e t h o d ( 5 ) c a n b e u s e d i n this case. I n the latter m e t h o d a l o g - l o g p l o t of

yi vs. Pi s h o u l d y i e l d a straight line. F i g u r e 1 presents results for n-alcohols a n d b e n z e n e f r o m t h e i s o b a r i c ( 7 6 0 m m H g )
Coates (6).
d a t a of W e h e a n d
R e l i a b l e infinite d i l u t i o n a c t i v i t y coefficients are established
for the o t h e r -alcohols f r o m d a t a for at least t w o , a n d p r e f e r a b l y three, of

t h e m . T h e s e y
or W i l s o n (7)
values are u s e d w i t h equations l i k e those of V a n L a a r

to generate a c t i v i t y coefficients
at i n t e r m e d i a t e
composi
tions a n d to c h e c k for a n e x i s t i n g a z e o t r o p e o r a difficult separation

c u r v e close to t h e 45
(x-t/
line).
F r o m the t w o series the one of t h e alcohols is p r e f e r r e d because here

acetone is the o v e r h e a d p r o d u c t a n d u s i n g a ketone causes the
v o l a t i l i t y to invert.
Scheibel (3)
recommends
relative
that the lowest b o i l i n g
h o m o l o g , w h i c h does not f o r m a n azeotrope, is chosen.
An
alternative
a p p r o a c h suggests the h o m o l o g w h i c h b a r e l y meets the m i s c i b i l i t y re

q u i r e m e n t , for this results i n h i g h selectivity
(8).
T h e choice between
these c o n f l i c t i n g suggestions m u s t b e m a d e o n the basis of
economical
considerations.
Hydrocarbon Mixtures. H e r e i t is u s u a l l y n o t the existence of a n
azeotrope b u t r a t h e r the close v a p o r pressure of the k e y
components
that often necessitates u s i n g extractive d i s t i l l a t i o n .

T h e q u a l i t a t i v e c r i t e r i a for solvent selection for h y d r o c a r b o n
tures h a v e b e e n d i s c u s s e d b y P r a u s n i t z a n d A n d e r s o n ( 9 )
a n d P r a u s n i t z (10).
(II),
and
mix
Weimer
S i n c e a r e v i e w was p r e s e n t e d r e c e n t l y b y Tassios
o n l y the c o n c l u s i o n s are discussed here.
T h e types of possible interactions b e t w e e n a m i x t u r e of h y d r o c a r b o n s

a n d a p o l a r solvent are:

4.
Extractive
TASSIOS
Distillation
49
Solvents
1. p h y s i c a l ( d i s p e r s i o n a n d d i p o l e - i n d u c e d d i p o l e )
2. c h e m i c a l ( r e s u l t i n g f r o m t h e f o r m a t i o n of l o o s e l y b o u n d aggre
gates)
U s i n g p h y s i c a l i n t e r a c t i o n alone, P r a u s n i t z a n d A n d e r s o n ( 9 ) a n d
W e i m e r a n d P r a u s n i t z (10)
h a v e d e v e l o p e d this s i m p l i f i e d expression
for h y d r o c a r b o n selectivity, S 3, at infinite d i l u t i o n i n a solvent:

2
lnS2s
oc ( r x W e - V a )
(3)
w h e r e is the p o l a r cohesive e n e r g y d e n s i t y of the solvent, w h i c h is rer e l a t e d to the p o l a r i t y a n d t h e m o l a r v o l u m e of t h e solvent. References 10

a n d 11 e x p l a i n h o w to c a l c u l a t e . T h e s e l e c t i v i t y is h i g h e r , t h e l a r g e r the
difference i n m o l a r v o l u m e b e t w e e n the h y d r o c a r b o n s a n d the l a r g e r the
p o l a r cohesive e n e r g y d e n s i t y ( ) of t h e solvent. P r a u s n i t z a n d c o w o r k e r s
(9, 10),
Gerster a n d his coworkers (12), Pierroti, D e a l , a n d D e r r
a n d D e a l a n d D e r r (14)
conclusions.
F o r e x a m p l e , the selectivities of the p a i r h e x a n e - b e n z e n e
at 2 5 C w i t h v a r i o u s solvents (14)
for
(13),
g i v e e x p e r i m e n t a l e v i d e n c e to s u p p o r t the a b o v e
are p r e s e n t e d a l o n g w i t h the values
i n T a b l e I I a n d p l o t t e d against e a c h other i n F i g u r e 2.
Here
3.0L.
l.ol
5.0
I
6.0
I
7.0
lnP
Figure 1. Prediction of infinite dilution activity coefficients for numbers of a

homologous series m a common solvent: n-Alcohols in Benzene at 1 atm
A 7B
vs. PB
7A vs. PA

50
E X T R A C T I V E
A N D
A Z E O T R O P I C
DISTILLATION
( V 3 - V 2 ) is constant, a n d the s e l e c t i v i t y tends to increase w i t h ,
indi
c a t e d b y E q u a t i o n 3.
L o o s e l y b o u n d aggregates ( c h e m i c a l effects) are f o r m e d w i t h the
h y d r o c a r b o n s a c t i n g as e l e c t r o n d o n o r s ( L e w i s b a s e ) a n d t h e
acting
as
electron
acceptors
(Lewis
acid).
The
forms the m o s t stable c o m p l e x w i t h the solvent experiences a

i n volatility.
E l e c t r o n donors
are r a t e d b y
solvents
hydrocarbon
that
decrease
ionization potential,
e l e c t r o n acceptors are r a t e d b y t h e i r e l e c t r o n affinities.
The
and
selectivity
w i l l b e h i g h e r , the l a r g e r the difference i n i o n i z a t i o n p o t e n t i a l b e t w e e n the

h y d r o c a r b o n s a n d the l a r g e r the e l e c t r o n affinity of the solvent
While
data
(15, 16),
on
ionization potentials
of
hydrocarbons
can be
(9).
found
e l e c t r o n affinities d a t a are r a r e because of difficulties i n t h e i r
experimental
determination.
Prausnitz and Anderson
that the s i g m a scale, p r o p o s e d b y H a m m e t t (17),
(8)
b e u s e d to
recommend
determine
a p p r o x i m a t e l y the s o l v e n t s r e l a t i v e a b i l i t y to f o r m complexes w i t h the

two hydrocarbons.
A t t e m p t s b y this a u t h o r , h o w e v e r , to use this scale
w e r e n o t c o n c l u s i v e . P r a u s n i t z a n d A n d e r s o n (8)
s h o u l d b e c o n s u l t e d to
u n d e r s t a n d better the p h y s i c a l a n d c h e m i c a l effects.

The Effect of Solvent and Solute Concentration. T h e effect of solvent
c o n c e n t r a t i o n o n selectivity is q u a l i t a t i v e l y d e s c r i b e d b y three types
(2,
11 ) s h o w n i n F i g u r e 3.
I n the first t y p e the s e l e c t i v i t y increases a l m o s t l i n e a r l y w i t h solvent
c o n c e n t r a t i o n , a n d this seems to represent the p r e d o m i n a n t p a t t e r n
19).
(18,
I n the s e c o n d t y p e the s e l e c t i v i t y increases m o r e t h a n l i n e a r l y w i t h
solvent c o n c e n t r a t i o n , b u t it is h a l t e d b y i m m i s c i b i l i t y at h i g h solvent
c o n c e n t r a t i o n s (20).
T h e t h i r d t y p e shows a m a x i m u m a n d is a n u n u s u a l
p a t t e r n . O n e s u c h case was o b s e r v e d b y H e s s et al. (21)
i n s t u d y i n g the
s e p a r a t i o n of 1-butane f r o m butenes-2 w i t h the f u r f u r a l solvent

Table II.
(96.5%
Selectivities and Polar Cohesive Energy Densities for the

Hexane ( l ) - B e n z e n e (2) System at 25C (12)
Solvent
M E K
Acetone
Pyridine
Aniline
Acetonitrile
Propionitrile
Nitromethane
Nitrobenzene
Phenol
Furfural
Dimethyl-sulfoxide
D i m e t h y l formamide
S2J
3.6
3.8
5.2
12.2
9.4
6.5
15.0
5.8
6.0
10.9
22.0
12.5
T (cal/cc)
5.33
6.14
3.71
6.37
8.98
7.17
9.44
4.89
9.84
7.62
9.47
8.07

4.
TASSIOS
Extractive
Distilfotion
51
Solvents
1.4
1.2
1/1
1.0
0.8
0.6
20
40
60
80
I g.molel
Figure
2.
Variation of selectivity with solvent's polar cohesive

system: hexane (l)-benzene (2) at 25C (12)
weight furfural and 3 . 5 % water).

that
selectivity
H o w e v e r , G e r s t e r et al
i n c r e a s e d w i t h solvent
c o n c e n t r a t i o n for
density;
(22)
report
the
system
b u t a n e - b u t e n e - 1 w i t h p u r e f u r f u r a l as solvent. C o n s i d e r i n g the extensive

e x p e r i m e n t a l w o r k of the s e c o n d s t u d y , the results s h o u l d b e c o n s i d e r e d
m o r e r e l i a b l e . A n o t h e r case i n v o l v e s the s e p a r a t i o n of e t h y l b e n z e n e f r o m
e t h y l c y c l o h e x a n e w i t h h e x y l e n e g l y c o l as solvent ( 2 3 ) .
The maximum
appears i n this case i f definite, a n d t h e d a t a are r e p r o d u c e d . T h i s decrease

i n s e l e c t i v i t y at h i g h e r solvent c o n c e n t r a t i o n results f r o m the
higher
temperatures r e s u l t i n g f r o m l a r g e r solvent c o n c e n t r a t i o n , for as t e m

p e r a t u r e increases, s e l e c t i v i t y decreases.
S e l e c t i v i t y is also affected b y the r e l a t i v e concentrations of the k e y
c o m p o n e n t s . If c o m p o n e n t ( 1 ) forms a m o r e n o n i d e a l s o l u t i o n w i t h t h e
solvent t h a n c o m p o n e n t ( 2 ) , a decrease i n Xi w i l l affect y m u c h m o r e
t h a n a decrease of x w i l l affect y .
2
more rapidly than w h e n x
H e n c e , as X i decreases, i2 increases
decreases.
Experimental evidence
(19,
20)
c l e a r l y shows this. F o r e x a m p l e , c o n s i d e r h o w p r o p a n o l affects the r e l a

tive v o l a t i l i t y of the n-hexane ( l ) - b e n z e n e ( 2 )
system. H e x a n e forms a

52
E X T R A C T I V E
0 0
0.2
04
0.0
02
0.4
Figure
A N D
A Z E O T R O P I C
Solvent Mole Fraction

06
08
0.6
Solvent V o l u m ^
1 0
0 8
y d r e e
1.0
V
3. Variation
of refotive volatility
with solvent
Hydrocarbon
ratio is 1:1. P: Constant.
ethylcyclohexane (l)-ethyl
DISTILLATION
amount.
benzene (2)/hexylene glycol (22)
A n-hexane (l)-~benzene (2)/l-propanol (18)

2-4 dimethylpentane (l)-benzene (2)/aniline (19)
m o r e n o n i d e a l system w i t h p r o p a n o l t h a n b e n z e n e
(xi/xo)
(19).
A s the r a t i o
decreases, Si increases. T h i s w a s o b s e r v e d e x p e r i m e n t a l l y
2
(19)
(see F i g u r e 4 ) .
Mixed Solvents Effect.
U s i n g m i x e d solvents c a n i m p r o v e selectivity.
F o r e x a m p l e , a d d i n g s m a l l a m o u n t s o f w a t e r has i m p r o v e d the selectivity

of f u r f u r a l i n s e p a r a t i n g C
(25)
h y d r o c a r b o n s (24). B a u m g a r t e n a n d G e r s t e r
h a v e s t u d i e d h o w v a r i o u s solvents affect the selectivity o f f u r f u r a l
for t h e p e n t a n e - p e n t e n e p a i r . T h e y c o n c l u d e d t h a t for o n l y a f e w solvents

some i m p r o v e m e n t w a s o b s e r v e d .
T h e r e s u l t i n g s e l e c t i v i t y lies b e t w e e n
t h e s e l e c t i v i t y of the p u r e solvents ( see T a b l e III ). T o a v o i d i m m i s c i b i l i t y

at h i g h solvent c o n c e n t r a t i o n s , a s e c o n d solvent is sometimes a d d e d
(25).
The Effect of Temperature. T h e t e m p e r a t u r e effect o n s e l e c t i v i t y is

given by:

4.
Extractive
TASSIOS
Distilfotion
53
Solvents
d(logS )
12
tf(l/T)
L \ - L \
2.303R
'
w h e r e L is p a r t i a l m o l a r heat of s o l u t i o n , c o m p o n e n t k at infinite d i l u
t i o n i n the solvent.
k
F o r h y d r o c a r b o n pairs i n different solvents a n d over m o d e r a t e t e m

p e r a t u r e ranges (to 1 0 0 C ) , a l i n e a r d e p e n d e n c y of l o g S i o n ( 1 / T )
c a n b e a s s u m e d (12, 14, 26). A n e x a m p l e is s h o w n i n F i g u r e 5, w h e r e
l o g S for t h e h e x a n e - b e n z e n e p a i r i n five different solvents is p l o t t e d
against t h e r e c i p r o c a l absolute temperature. T h e r e l a t i o n s h i p c a n b e
c o n s i d e r e d l i n e a r for e n g i n e e r i n g a p p l i c a t i o n s . S e l e c t i v i t y decreases w i t h
i n c r e a s i n g temperature, a n d this explains t h e u n u s u a l m a x i m u m i n t h e
v a r i a t i o n of selectivity w i t h solvent c o n c e n t r a t i o n s h o w n b y t h e system
e t h y l b e n z e n e - e t h y l c y c l o h e x a n e w i t h h e x y l e n e g l y c o l as solvent ( F i g
ure 3 ) .
2
30
i.ol
0.0
02
04
0.6
1
0 8
1.0
M. Van Winkle, "Distillation," McGraw-Hill

Figure 4. Variation of relative volatility with composition (2). Sys
tem: hexane (l)-benzene (2)/l-propanol (3) at 760 mm (18).
x,/x :
2
1:3, A
1:1,
3:1

54
E X T R A C T I V E
Table III.
Mixed
1-Pentene(2)
P r o p a n e (3)
P r o p y l e n e (2)
A Z E O T R O P I C
DISTILLATION
Selectivity of Pure and Mixed Solvents
Solute
n-Pentane(3)
A N D
Solvents
B;
Vol%
M e t h y l Cellosolve
Nitromethane
Nitromethane
Nitromethane
0
5
100
1.69
1.70
2.49
Pyridine
Pyridine
Pyridine
-Butyrolactone
-Butyrolactone
-Butyrolactone
0
32.1
100
1.60
1.79
2.17
E t h y l m e t h y l ketone
-Butyrolactone
-Butyrolactone
-Butyrolactone
100
50
0
2.17
1.79
1.62
Acetonitrile
Acetonitrile
Acetonitrile
Water
Water
Water
0
50
100
1.64
1.34
.98
Acetonitrile-water data from Reference 41, all others from Reference
Quantitative
Methods
Infinite d i l u t i o n a c t i v i t y coefficients are p r e d i c t e d b y several methods

(4,5,10,
27,28, 29, 30, 31).
method
(4),
method
(10),
T h e m o s t g e n e r a l are the P i e r o t t i - D e a l - D e r r
the p a r a c h o r m e t h o d
modified
(27),
a n d the
Weimer-Prausnitz
by Hellpinstill and V a n Winkle
a c c u r a c y is l i m i t e d i n these m e t h o d s
Since
(28).
a n d noninfinite dilution
tions p r e v a i l i n a c t u a l operations, the infinite d i l u t i o n a c t i v i t y
condi
coefficients
o b t a i n e d s h o u l d o n l y be u s e d for s c r e e n i n g purposes.
Pierotti-Deal-Derr Method (4).
()
Infinite d i l u t i o n a c t i v i t y
coefficients
of s t r u c t u r a l l y r e l a t e d systems are c o r r e l a t e d i n this m e t h o d to the
n u m b e r of c a r b o n atoms of the solute a n d solvent (n
m e m b e r s of the h o m o l o g o u s series H ( C H 2 )
w l
a n d n^).
F o r the
X i ( s o l u t e ) i n the m e m b e r s
of the h o m o l o g o u s series H ( C H ) Y 2 :
2
log o
y
l l
^ + ^
no
w h e r e the constants are functions of t e m p e r a t u r e , B

of t h e solvent series, C
of b o t h , a n d D
(5)
+ Dofa-n*)*
U\
2
and F
is a f u n c t i o n of the solute series, A
lt2
are f u n c t i o n s
is a f u n c t i o n
is i n d e p e n d e n t of b o t h .
F o r z e r o m e m b e r s of a seriese.g., w a t e r for a l c o h o l s n o infinite

v a l u e for y
is o b t a i n e d .
Instead, b y c o n v e n t i o n , a n y terms c o n t a i n i n g
a n for the z e r o m e m b e r are i n c o r p o r a t e d i n the c o r r e s p o n d i n g

cient. So for -alcohols i n w a t e r :

coeffi
4.
TASSIOS
Extractive
Distilhtion
l o g y\
Notice
= + B % +
2
that the t e r m D
(%-n )
constant because D
55
Solvents
was
(6)
CJn
i n c o r p o r a t e d i n t o the
is s m a l l e r t h a n the other coefficients b y a factor of
1 0 ; therefore, this t e r m is insignificant. I n E q u a t i o n 6 o n l y is a f u n c

3
t i o n of the solute a n d solvent, as stated before.
is a l w a y s the same
w h e n w a t e r is the solvent a n d C i is the same for -alcohol solutes.
This
is s h o w n better f r o m t h e f o l l o w i n g h o m o l o g o u s series i n w a t e r at 100C:

-Alcohols:
l o g y\
-0.420 +
(0.517)% +
(0.230)/%
-Aldehydes: l o g y = - 0 . 6 5 0 + ( 0 . 5 1 7 ) % + ( 0 . 3 2 ) / %
1
T h e coefficient is the same i n b o t h cases.

E q u a t i o n 6 assumes a different f o r m for c y c l i c c o m p o u n d s i n a
solvent.
F o r unalkylated cyclic (aromatic
and/or naphthenic)
fixed
hydro
c a r b o n s i n fixed solvents:
log y\
where
and B
+ Bn
are
solvent
+ Bn
+ C [l/r -
dependent
1]
constants, C
(8)
r
is
constant,
d e p e n d i n g o n the t y p e of ring ( d i p h e n y l l i k e or n a p h t h a l e n e l i k e ) , r is the

n u m b e r of rings, a n d n
bers, respectively.
a n d % are a r o m a t i c a n d n a p t h e n i c c a r b o n n u m
F o r e x a m p l e for d i p h e n y l l i k e h y d r o c a r b o n s i n p h e n o l
at 2 5 C :
logy\ =
0.383 + 0.1421 n + 0 . 2 4 0 6 n
a
1.845[l/r -
1]
30 I
(9)
1.0 I
I.JU
Figure 5. Dependence of selectivity on temperature.

System: hexane (1}benzene (2). nitrobenzene, A acetonitrile, + furfural, dimethyl
sulfolane,
diethylene glycol

56
E X T R A C T I V E
A N D AZEOTROPIC
DISTILLATION
C o r r e l a t i o n s f o r various systems, d e v e l o p e d b y u s i n g e x p e r i m e n t a l
d a t a o n 2 6 5 systems, are a v a i l a b l e ( I I , 2 6 ) . T h e r e l a t i o n s h i p s u s e d , the
n u m e r i c a l values o f t h e constants, a n d t h e c a l c u l a t e d a n d e x p e r i m e n t a l
values f o r y are a v a i l a b l e ( 1 3 ) a n d s h o u l d b e u s e d t o s t u d y solvent
selection.
The Parachor Method ( 2 7 ) . Infinite d i l u t i o n a c t i v i t y coefficients are
o b t a i n e d a c c o r d i n g to this m e t h o d f r o m the f o l l o w i n g r e l a t i o n s h i p ( 2 7 ) :
^-^^ - ^
10
1/2
(10)
w h e r e 17* is p o t e n t i a l e n e r g y o f c o m p o n e n t i c a l c u l a t e d f r o m : C7< =
( A H a p ) i R T , is e n t h a l p y o f v a p o r i z a t i o n , c a l / g r a m m o l e , C is a
constant, a f u n c t i o n o f temperature, t h e p a r a c h o r r a t i o o f the t w o c o m
ponents, a n d t h e n u m b e r o f c a r b o n atoms i n t h e solute a n d solvent
m o l e c u l e s ; R is t h e gas constant.
V
E q u a t i o n 10 generalizes t h e expression o f E r d o s ( 3 1 ) a p p l i c a b l e to
c o m p o n e n t s i n v o l v i n g t h e same f u n c t i o n a l g r o u p . R e t u r n i n g to t h e c o n
stant C i n E q u a t i o n 10, u s u a l l y t h e n u m b e r o f c a r b o n atoms does n o t
d i r e c t l y affect t h e constant. A p p a r e n t l y this effect is c o r r e c t e d b y t h e
p a r a c h o r w h i c h changes w i t h t h e n u m b e r of c a r b o n atoms. F o r example,
for aromatics i n f u r f u r a l :
C (0.5632 + 0.03 X 10" *) (Pi/P )
4
02222
(11)
a n d f o r naphthenes i n f u r f u r a l :
l o g C = (0.2658 + 14.53 X 10" ) (log P i / P
4
- 0.5982) - 0.2679 (12)
w h e r e P i is p a r a c h o r o f c o m p o n e n t i a n d t is temperature, C . A b o u t t h e
same v a r i e t y o f systems, c o v e r e d i n t h e P D D m e t h o d , is c o v e r e d i n this
a p p r o a c h , a n d t h e expressions f o r C are g i v e n elsewhere ( 2 7 ) .
A c o m p a r i s o n b e t w e e n t h e P D D a n d t h e p a r a c h o r m e t h o d seems to
suggest t h a t t h e latter is n o w o r s e t h a n t h e former, a n d often better ( 2 7 ) .
F o r t h e systems c o n s i d e r e d , t h e p a r a c h o r m e t h o d gives l o w e r m a x i m u m
deviations i n 11 cases, t h e P D D i n 7. A l s o , t h e authors o f t h e p a r a c h o r
m e t h o d c l a i m better a c c u r a c y w h e n e x t r a p o l a t i o n w i t h respect to tempera
ture is r e q u i r e d . F o r example, t h e case o f n-heptane ( 1 ) i n 1-butanol ( 2 )
is c i t e d . V a l u e s f o r y c a l c u l a t e d b y e x t r a p o l a t i n g t h e P D D constants
to temperatures r a n g i n g f r o m 114.5C-171.9C y i e l d error r a n g i n g f r o m
1 0 0 - 2 0 0 % ; t h e errors f o r t h e p a r a c h o r m e t h o d range b e t w e e n 0 . 5 - 3 . 6 % .
H o w e v e r , this is t h e o n l y c o m p a r i s o n a v a i l a b l e ( 2 7 ) a n d m a y n o t a l w a y s
b e v a l i d . T h e p a r a c h o r values are estimated f o r different c o m p o u n d s b y
a g r o u p c o n t r i b u t i o n m e t h o d (32, 33).
The Weimer-Prausnitz (WP) Method (10). S t a r t i n g w i t h t h e H i l d e b r a n d - S c h a t c h a r d m o d e l f o r n o n p o l a r mixtures (34), W e i m e r a n d P r a u s -

4.
Extractive
TASSIOS
DistiUation
Solvents
57
n i t z d e v e l o p e d a n expression for e v a l u a t i n g values of h y d r o c a r b o n s i n

p o l a r solvents:
R T lny
RT[
[( -
In V / V i +
2
2 ]
12
V2/V1]
1 -
(13)
w h e r e V * is t h e m o l a r v o l u m e of p u r e i, c c / g r a m m o l e , * is t h e n o n p o l a r
s o l u b i l i t y parameter, c o m p o n e n t i , a n d r is the p o l a r s o l u b i h t y p a r a m e t e r ,
{
c o m p o n e n t i . T h e s u b s c r i p t 1 represents the p o l a r solvent a n d s u b s c r i p t

2 is the h y d r o c a r b o n solute w i t h
f
1 2
fc'n
(14)
Later H e l p i n s t i l l and V a n W i n k l e (28)
suggested that E q u a t i o n 13
is i m p r o v e d b y c o n s i d e r i n g the s m a l l p o l a r s o l u b i l i t y p a r a m e t e r of
the
h y d r o c a r b o n (olefins a n d a r o m a t i c s ) :
RTZny
-V [(Ai - )
2
R T [ l n V2/V1 +
( -
*) 2
2 ]
12
V2/V1]
1 -
(13a)
A l s o E q u a t i o n 14 b e c o m e s :
12
1(
)
2
(14a)
T h e v a l u e of k was o b t a i n e d b y c u r v e - f i t t i n g e x p e r i m e n t a l
infinite
d i l u t i o n a c t i v i t y coefficients of paraffins, olefins, a n d aromatics i n several

p o l a r solvents.
Table IV.
T h e v a l u e of k for e a c h h y d r o c a r b o n g r o u p is g i v e n i n
T h e values for are t a k e n f r o m plots ( 2 8 ) .

{
c a l c u l a t i n g ^ is also a v a i l a b l e
T h e term
12
The method
for
(28).
corresponds to the i n d u c t i o n e n e r g y b e t w e e n the p o l a r
a n d n o n p o l a r , or s l i g h t l y p o l a r , species.
S i n c e n o c h e m i c a l effects
are
i n c l u d e d , the c o r r e l a t i o n s h o u l d not b e u s e d for solvents s h o w i n g s t r o n g

hydrogen bonding.
Rapid Experimental
Techniques
T h e safest m e t h o d u s e d to choose extractive d i s t i l l a t i o n solvents is

to m e a s u r e d i r e c t l y m u l t i c o m p o n e n t v a p o r - l i q u i d e q u i l i b r i u m d a t a of
the c o m p o n e n t s i n v o l v e d w i t h the solvents b e i n g c o n s i d e r e d . T h i s , h o w
ever, is a tedious, t i m e c o n s u m i n g a p p r o a c h . T h e r e are r a p i d e x p e r i m e n t a l
t e c h n i q u e s w h i c h c a n at least be u s e d i n the s c r e e n i n g stage of selecting
t h e solvent.
T w o m e t h o d s are d i s c u s s e d h e r e ; b o t h use g a s - l i q u i d c h r o
m a t o g r a p h y , a n d t h e y are s i m p l e a n d r a p i d . T h e first ( 3 5 )
to screen; the s e c o n d (36),
tive volatilities.
is o n l y u s e d
besides screening, gives infinite d i l u t i o n r e l a
B o t h methods
r e q u i r e a solvent w i t h a l o w e r
pressure t h a n the solutes as i n extractive d i s t i l l a t i o n .

vapor
58
E X T R A C T I V E
Values for k in Equation
Table IV.
DISTILLATION
(14a)
System
% Average
Absolute
Error in
Paraffins
Olefins
Aromatics
0.399
0.388
0.447
11.6
8.5
13.5
Screening Solvents through G L C . I n g a s - l i q u i d

(GLC)
separating mixture components
l i q u i d b e i n g a b l e to i n t e r a c t w i t h different
w i t h t h e v a p o r pressure differences.
chromatography
is b a s e d o n the p a r t i t i o n i n g
strengths w i t h t h e m , a l o n g
T h e same is true for a n extractive
d i s t i l l a t i o n solvent. It seems l o g i c a l , therefore, that extractive d i s t i l l a t i o n

solvents c o u l d b e r a t e d o n t h e i r p e r f o r m a n c e as p a r t i t i o n i n g l i q u i d s w i t h
the m i x t u r e u n d e r c o n s i d e r a t i o n .
W a r r e n et al. (37)
a n d Sheets a n d M a r c h e l l o (38)
have
suggested
u s i n g g a s - l i q u i d c h r o m a t o g r a p h y to s t u d y extractive d i s t i l l a t i o n solvents.
I n t h e first s t u d y (37) a n i n d i v i d u a l c o l u m n w a s p r e p a r e d f o r e a c h solvent
b y u s i n g this solvent as a p a r t i t i o n i n g l i q u i d .
It is a tedious,
time-
c o n s u m i n g m e t h o d a n d w a s r e s t r i c t e d to solvents o f h i g h b o i l i n g p o i n t .
F i n a l l y t h e e x p e r i m e n t a l e v i d e n c e b a s e d o n l i m i t e d d a t a is n o t c o n c l u s i v e .
Sheets a n d M a r c h e l l o (38)
significantly s i m p l i f i e d i t b y r e p l a c i n g t h e
p r e p a r i n g o f i n d i v i d u a l c o l u m n s f o r e a c h solvent w i t h d i r e c t l y i n j e c t i n g
the solvent i n a c h r o m a t o g r a p h c o n t a i n i n g a g e n e r a l p u r p o s e c o l u m n .
N o e x p e r i m e n t a l e v i d e n c e w a s g i v e n to s u p p o r t a p p l y i n g G L C t o rate
extractive d i s t i l l a t i o n solvents.
R e c e n t l y Tassios
( 3 5 ) has p r o v e d
that
the m e t h o d is effective for screening.

T h e t e c h n i q u e consists o f i n j e c t i n g a c e r t a i n a m o u n t (e.g., 3 c c ) of
the solvent b e i n g c o n s i d e r e d i n t o the c h r o m a t o g r a p h c o n t a i n i n g a g e n e r a l
p u r p o s e c o l u m n o r a c o l u m n c o n t a i n i n g a n inert s u p p o r t . N e x t , f o u r o r
five 5 - m l samples o f a m i x t u r e of t h e k e y c o m p o n e n t s are injected, a n d
t h e s e p a r a t i o n factor, F ,
12
is m e a s u r e d f o r e a c h s a m p l e :
F
12
(15)
= D />i
2
w h e r e D is distance b e t w e e n a i r p e a k a n d p e a k f o r c o m p o n e n t i as s h o w n
{
i n F i g u r e 6.
T h e o b t a i n e d values o f F
12
f o r these samples a r e p l o t t e d
against
t i m e f r o m solvent injection to establish t h e m a x i m u m v a l u e f o r t h e sepa

r a t i o n factor, F12 ( m a x ) .
F u r t h e r details a b o u t t h e e x p e r i m e n t a l t e c h
n i q u e are i n t h e o r i g i n a l p a p e r ( 3 5 ) . T h e larger t h e v a l u e o f F
12
(max),
the better t h e solvent c a n separate t h e m i x t u r e , i n d i c a t i n g a better ex

t r a c t i v e d i s t i l l a t i o n solvent.
T h i s w a s v e r i f i e d b y c o m p a r i n g values f o r
F12 ( m a x ) a n d infinite d i l u t i o n r e l a t i v e v o l a t i l i t i e s ( i 2 ) for t h e system

n-hexanebenzene
w i t h six different solvents.
T h e results p r e s e n t e d i n

4.
TASSIOS
Extractive
Distilhtion
59
Solvents
1
Figure 6.
Evaluation
of the separation
factor
Fjg
T a b l e V a n d p l o t t e d i n F i g u r e 7 suggest t h a t the l a r g e r the v a l u e of

ai2, the l a r g e r the v a l u e of F
(max).
12
T h e deviations observed w i t h
d i e t h y l e n e g l y c o l m u s t r e s u l t f r o m the l i m i t e d s o l u b i l i t y of n-hexane a n d
benzene i n this solvent ( 3 5 ) .
C o m p a r i n g the solvents b a s e d o n the same
v o l u m e is r e c o m m e n d e d because i t is easier a n d seems m o r e c o n c l u s i v e .

Infinite Dilution Relative Volatilities through G L C . If the solvent
a m o u n t injected i n the c o l u m n is h i g h e n o u g h so t h a t i n f i n i t e d i l u t i o n
c o n d i t i o n s for the i n j e c t e d solute p r e v a i l , it is r e a d i l y s h o w n ( 3 8 )
the s e p a r a t i o n factor
becomes
e q u a l to the infinite d i l u t i o n
that
relative
volatility:
(16)
<x ij =
D o r i n g ( 3 9 ) has s h o w n t h a t infinite d i l u t i o n r e l a t i v e v o l a t i l i t i e s c a n
b e e v a l u a t e d t h r o u g h G L C . H e p r e p a r e d a s p e c i a l c o l u m n for
solvent u n d e r c o n s i d e r a t i o n , a tedious project.
M a r c h e l l o (38)
each
A y e a r l a t e r Sheets a n d
s h o w e d t h a t s e p a r a t i o n factors increase w i t h i n c r e a s e d
a m o u n t s of injected solvent. L a t e r Tassios ( 3 5 )
f o u n d o u t the same to
Table V .
Separation Factors and Infinite Dilution Relative Volatilities
for the System w-Hexane ( l ) - B e n z e n e (2) at 67C (35)
Fj2
Solvent
Pyridine
Propionitrile
Furfural
Nitromethane
N-methylpyrrolidone
Diethyleneglycol
a
12
3.70
4.80
6.55
7.00
8.20
9.10
0.03 gram
moles
5.85
6.10
6.40
6.95
8.40
4.70
Calculated for two solvent amounts.

Sec
5.40
6.40
7.50
7.95
8.40
4.50
60
E X T R A C T I V E
A N D
A Z E O T R O P I C
DISTILLATION
b e true b u t o b s e r v e d that at h i g h e r solvent amounts, 5 - 6 c c for the c o l u m n u s e d i n that s t u d y , the separation factor seems to l e v e l off a p p r o a c h i n g the infinite d i l u t i o n v a l u e w h i c h was f o u n d f r o m static measurements.
I n a later s t u d y Tassios (36)
u s e d a 6 ft c o l u m n c o n t a i n i n g o n l y c h r o m o -
sorb G a n d a 10 ft c o l u m n c o n t a i n i n g glass beads a n d f o u n d t h a t constant

values for the separation factor w e r e o b t a i n e d at solvent levels e q u a l or
a b o v e 2.0 cc. F o r four solvents w i t h t w o h y d r o c a r b o n b i n a r y m i x t u r e s ,
the separation factor m e a s u r e d at 2 c c of solvent agree w e l l w i t h e x p e r i m e n t a l infinite d i l u t i o n relative volatilities. T h e m a x i m u m d e v i a t i o n was
2 3 . 8 % , the m i n i m u m 3 . 1 % .
T h i s a p p r o a c h of d i r e c t solvent
injection
eliminates the tedious c o l u m n p r e p a r a t i o n .
C*2
Hydrocarbon Processing
Figure 7. Relationship
between maximum separation factors and
infinite dilution rehtive volatilities for the system:
n-hexane-benzene
with various solvents at 67C (35)

4.
TASSIOS
Figure
Extractive
8.
Distilfotion
Variation
61
Solvents
of selectivity with solvent's

energy density
propane (l)-propene
pentane (l)-pentene
J . butyronitrile
2. acetone
4. acetonitrile
5. furfural
polar
cohesive
(2) at 27C
(24)
(2) at 25C
(10)
3. propionitrile
6. DMF
LHscussion
T h e c r i t e r i o n of h i g h solvent p o l a r i t y s h o u l d b e c a u t i o u s l y a p p l i e d
( E q u a t i o n 3 ) i n p r e p a r i n g a list o f p r o s p e c t i v e
solvents.
There are
exceptions a m o n g solvents s h o w i n g h y d r o g e n b o n d i n g w h i c h p r o d u c e s
h i g h e r values o f p o l a r cohesive energy d e n s i t y t h a n t h e p h y s i c a l i n t e r a c
tions alone. T h i s explains, f o r example, t h e r e l a t i v e l y l o w selectivities o b
s e r v e d w i t h t h e t w o ketones a n d p h e n o l ( T a b l e I I a n d F i g u r e 2 ) . H a n s o n
a n d V a n W i n k l e (40)
m a d e a s i m i l a r o b s e r v a t i o n for 2 - b u t a n o l w i t h t h e
binary hexane-hexene-1.
A s a general
r u l e solvents
showing
strong
h y d r o g e n b o n d i n g affect l o w selectivities. A n o t h e r e x c e p t i o n to t h e a b o v e
c r i t e r i o n is p r e s e n t e d i n F i g u r e 8 w h e r e In S f o r t h e p r o p y l e n e - p r o p a n e
p a i r w i t h six different solvents at 2 7 C (41)
is p l o t t e d against . D e
2
c r e a s i n g selectivity tends to o c c u r w i t h i n c r e a s i n g solvent p o l a r cohesive

energy density.
I n t h e same figure t h e d a t a o n p e n t a n e - p e n t e n e
(12)
w i t h t h e same solvents a r e also p l o t t e d . H e r e a c l e a r t r e n d of i n c r e a s i n g

selectivity w i t h i n c r e a s i n g solvent p o l a r cohesive energy d e n s i t y is o b -

62
E X T R A C T I V E
served.
DISTILLATION
Because of the similarity between t h e t w o hydrocarbon
pairs
a n d because the d a t a o n the C p a i r are s u p p o r t e d b y f u r t h e r e x p e r i m e n t a l

5
evidence ( 3 9 ) , the C data are of questionable accuracy.

3
T h e p r e d i c t i v e t e c h n i q u e s a r e r a t h e r accurate.
H o w e v e r , significant
errors h a v e b e e n o b s e r v e d i n f e w cases (4, 13, 27, 40).
N o direct com
p a r i s o n b e t w e e n t h e three p r e d i c t i v e m e t h o d s is a v a i l a b l e .
T h e authors
of the p a r a c h o r m e t h o d (27) c l a i m that t h e i r m e t h o d y i e l d s e q u a l o r better

results t h a n t h e P D D m e t h o d f o r t h e cases c o n s i d e r e d i n t h e i r s t u d y ; i t is
b e l i e v e d (42),
mended.
h o w e v e r , that t h e latter is m o r e r e l i a b l e a n d i t is r e c o m
T h e Weimer-Prausnitz
m e t h o d p r o b a b l y gives less a c c u r a c y
t h a n t h e P D D m e t h o d , b u t i t is m o r e general.
F o r example, H a n s o n a n d
V a n W i n k l e (40) r e p o r t t h a t t h e i r d a t a o n t h e h e x a n e - h e x e n e p a i r w e r e
not successfully c o r r e l a t e d
b y the W P method.
W i n k l e m o d i f i c a t i o n is r e c o m m e n d e d
N u l l a n d P a l m e r (43)
The Helpinstill-Van
over t h e W P method.
Recently,
h a v e presented a m o d i f i c a t i o n o f t h e W P m e t h o d
w h i c h p r o v i d e s better a c c u r a c y b u t i t is less general.
The P D D
method
s h o u l d b e u s e d c a u t i o u s l y w h e n e x t r a p o l a t i o n w i t h respect t o t e m p e r a
t u r e is u s e d (27).
expected.
mended
W h e n t h e G L C m e t h o d is u s e d , r e l i a b l e results are
E v a l u a t i o n of infinite d i l u t i o n relative v o l a t i l i t i e s is r e c o m
(36).
Literature Cited
1. Berg, L., Chem. Eng. Progr. (1969) 65, 9, 52.
2. Van Winkle, M., "Distillation," p. 436, McGraw-Hill, New York, 1968.
3. Scheibel, E. G., Chem. Eng. Progr. (1948) 44, 927.
4. Pierotti, G. I., Deal, C. H., Derr, E. L., Ind. Eng. Chem. (1955) 51, 95.
5. Tassios, D. P., Van Winkle, M.,J.Chem. Eng. Data (1967) 12, 555.
6. Wehe, A. H., Coates, J., A.I.Ch.E. J. (1955) 2, 241.
7. Orye, R. V., Prausnitz, J., Ind. Eng. Chem. (1965) 57, 96.
8. Oliver, E. D., "Diffusional Separation Processes: Theory, Design and Evalu
ation," p. 189, Wiley, New York, 1966.
9. Prausnitz, J. M., Anderson, R., A.I.Ch.E. J. (1961) 7, 96.
10. Weimer, R. F., Prausnitz, J., Petrol. Refiner (1965) 44, 9, 237.
11. Tassios, D. P., Chem. Eng. (1969) 76, 3, 118.
12. Gerster, J. ., Gordon, J., Eklund, R. B.,J.Chem. Eng. Data (1960) 5, 423.
13. Pierotti, G. I., Deal, C. H., Derr, E. L., Document No. 5782, American
Documentation Institute, Washington, D. C., 1958.
14. Deal, C. H., Derr, E. L., Ind. Eng. Chem. Process Design Develop. (1964)
3, 394.
15. Prausnitz, J. M., "Molecular Thermodynamics of Fluid-Phase Equilibria,"
p. 63, Prentice-Hall, Englewood Cliffs, 1969.
16. Watanabe, K.,J.Chem. Phys. (1954) 22, 1564.
17. Hammet, L. P., "Physical Organic Chemistry," McGraw-Hill, New York,
1940.
18. Murti, P. S., Van Winkle, M., A.I.Ch.E. J. (1957) 3, 517.
19. Prabhu, P. S., Van Winkle, M., J. Chem. Eng. Data (1963) 8, 14, 210.
20. Stephenson, R. W., Van Winkle, M.,J.Chem. Eng. Data (1962) 7, 510.
21. Hess, . V., et al., "Phase Equilibrium," Amer. Inst. Chem. Engrs. Symp.
Ser. 2 (1962) 72-79.

4.
TASSIOS
Extractive Distillation Solvents
63
22. Gerster, J. ., Mertes, T. S., Colburn, A. P., Ind. Eng. Chem. (1947) 39,
797.
23. Quozati, ., Van Winkle, M., J. Chem. Eng. Data (1960) 5, 269.
24. Jordan, D., Gerster, J. ., Colbum, A. P., Nohl, K., Chem. Eng. Progr.
(1950) 46, 601.
25. Baumgarten, P. K., Gerster, J. ., Ind. Eng. Chem. (1964) 46, 2396.
26. Mertes, T. S., Colburn, A. P., Ind. Eng. Chem. (1947) 39, 787.
27. Balakrishnan, S., Krishnan, V., International Symp. on Distillation (1969),
p. 49, Inst. Chem. Eng., Brighton, England.
28. Helpinstill, J. G., Van Winkle, M., Ind. Eng. Chem. Process Design De
velop. (1968) 7, 213.
29. Wilson, G. M., Deal, C. H., Ind. Eng. Chem. Fundamentals (1962) 1, 20.
30. Deal, C. H., Derr, E. L., Papadopoulos, M. N., Ind. Eng. Chem. Funda
mentals (1962) 1, 17.
31. Erdos, E., Collection Czech. Chem. Commun. (1956) 21, 1521.
32. Quale, O. R., Chem. Rev. (1953) 53, 439.
33. Reid, R. C., Sherwood, T. K., "The Properties of Gases and Liquids," p. 373,
McGraw-Hill, New York, 1966.
34. Hildebrand, T. H., "Solubility of Non-Electrolyles," p. 131, Dover, New
York, 1964.
35. Tassios, D. P., Hydrocarbon Process. Petrol. Refiner (1970) 49, 7, 114.
36. Tassios, D. P., Ind. Eng. Chem. Process Design Develop. (1972) 11, 43.
37. Warren, G. W., Warren, R. R., Yarborough, V. ., Ind. Eng. Chem. (1959)
51, 1475.
38. Sheets, M. R., Marchello, J. M., Petrol. Refiner (1963) 42, 99.
39. Doring, C., Z. Chem. (1961) 1, 347.
40. Hanson, D. O., Van Winkle, M.,J.Chem. Eng. Data (1967) 12, 319.
41. Hafslund, E. R., Chem. Eng. Progr. (1969) 65, 9.
42. Prausnitz, J. M., private communication, 1970.
43. Null, H. R., Palmer, D. ., Chem. Eng. Progr. (1969) 65, 9, 47.

5
Azeotropic Distillation Results from
Automatic Computer Calculations
CLINE BLACK, R. A. GOLDING, and D. E. DITSLER
Shell Development Co., Emeryville, Calif. 94608
In azeotropic distillation the added component, or entrainer,

is taken overhead with one of two or more components
being separated in a distillation column. If a second liquid
phase forms upon condensing the overhead vapors, the
entrainer-rich phase is refluxed or recycled back to the col
umn. The other liquid phase is discarded, recycled to some
suitable point in the plant, or processed further to recover
dissolved components before being discarded. Methods pre
sented earlier by one of the authors are applied to calculate
two and three phase equilibria required in a computer pro
gram for calculating azeotropic distillations. A brief descrip
tion of the program is given; a sample output is listed and
described. Calculated results for dehydrating aqueous etha
nol mixtures are compared for the entrainers, n-pentane,
benzene, and diethyl ether. Column flows, heat loads, and
stage requirements are lowest for n-pentane. The entrain
ers are rated in decreasing order of suitability: n-pentane,
benzene, and diethyl ether.
T ^ V i s t r i b u t i o n of c o m p o n e n t s b e t w e e n separable phases is the basis for

**** most c o m m o n l y u s e d separation methods. R e g a r d l e s s of the t y p e of
s e p a r a t i o n step, its d e s i g n d e p e n d s o n accurate d i s t r i b u t i o n coefficients
for the c o m p o n e n t s b e t w e e n the c o n t a c t i n g phases.
T h e s e are g i v e n i n
c o m p o s i t i o n s or m o r e f u n d a m e n t a l properties of the e q u i l i b r i u m phases.

In
d i s t i l l a t i o n the c o m p o n e n t s are d i s t r i b u t e d b e t w e e n
v a p o r a n d l i q u i d phases.
separable
T h e d i s t r i b u t i o n coefficients or values are
the ratios o f the v a p o r - l i q u i d c o m p o s i t i o n s i n the e q u i l i b r i u m
phases.
T h e y are expressed as the l i q u i d phase a c t i v i t y coefficients, / s , the v a p o r

64
5.
BLACK,
GOLDiNG,
Computer
A N D DITSLER
65
Calcufotions
pressures of t h e p u r e c o m p o n e n t s * s, t h e t o t a l pressure P, a n d t h e
i m p e r f e c t i o n - p r e s s u r e coefficients 0/s, as
T h e r e l a t i v e d i s t r i b u t i o n of c o m p o n e n t s i a n d ; is
an = KJKt
yiP , / *
4
(2)
A z e o t r o p i c d i s t i l l a t i o n is a c c o m p l i s h e d b y a d d i n g t o t h e l i q u i d p h a s e
a v o l a t i l e t h i r d c o m p o n e n t w h i c h changes t h e v o l a t i l i t y o f o n e of t h e t w o
c o m p o n e n t s m o r e t h a n t h e other, so t h e c o m p o n e n t s a r e s e p a r a t e d b y
d i s t i l l a t i o n . T h e t w o c o m p o n e n t s to b e s e p a r a t e d often are close b o i l i n g
c o m p o n e n t s w h i c h d o o r d o n o t azeotrope i n t h e b i n a r y m i x t u r e , b u t
sometimes t h e y are c o m p o n e n t s w h i c h d o a z e o t r o p e a l t h o u g h t h e y a r e
n o t close b o i l i n g c o m p o n e n t s .
T h e a d d e d t h i r d c o m p o n e n t , sometimes c a l l e d the entraner, m a y
f o r m a t e r n a r y azeotrope w i t h the t w o c o m p o n e n t s b e i n g separated.
H o w e v e r , i t m u s t b e sufficiently v o l a t i l e f r o m t h e s o l u t i o n so t h a t i t is
t a k e n o v e r h e a d w i t h one of the t w o c o m p o n e n t s i n the d i s t i l l a t i o n .
If
the entraner a n d the c o m p o n e n t t a k e n o v e r h e a d separate i n t o t w o l i q u i d

phases w h e n the v a p o r o v e r h e a d is c o n d e n s e d , t h e entraner p h a s e is
refluxed b a c k to the c o l u m n . T h e other phase c a n b e f r a c t i o n a t e d t o
r e m o v e the d i s s o l v e d entraner a n d the r e s i d u a l a m o u n t of the o t h e r
c o m p o n e n t before i t is d i s c a r d e d . A l t e r n a t i v e l y , this s e c o n d l i q u i d p h a s e
is r e c y c l e d to some a p p r o p r i a t e p l a c e i n t h e m a i n process scheme.
A z e o t r o p i c d i s t i l l a t i o n has often b e e n d i s c u s s e d i n recent l i t e r a t u r e
( J , 2, 3 ) .
M e t h o d s for p r o v i d i n g phase e q u i l i b r i a f o r a z e o t r o p i c a n d
extractive d i s t i l l a t i o n h a v e b e e n s t u d i e d extensively ( J , 4, 5, 6, 7,
8,9).
S o m e h a v e d i s c u s s e d the d e s i g n ( J O ) o r c a l c u l a t i o n of a z e o t r o p i c d i s t i l l a tions ( 2 , 3 ) ; others o n l y d i s c u s s e d c h o o s i n g t h e entraner for a z e o t r o p i c

d i s t i l l a t i o n processes
(11).
A n u n d e r s t a n d i n g of the phase e q u i l i b r i a i n v o l v e d is also v i t a l i n

c h o o s i n g the entraner.
T h i s not only depends on k n o w i n g the pure
c o m p o n e n t v a p o r pressures b u t also k n o w i n g n o n i d e a l i t i e s of the c o m ponents i n the l i q u i d a n d v a p o r phases.

T h e m e t h o d s u s e d here to g i v e t h e phase e q u i l i b r i a are r e v i e w e d , a n d
the A z e o t r o p i c D i s t i l l a t i o n P r o g r a m A D P / A D P L L E is d e s c r i b e d . A p p l i c a t i o n of the p r o g r a m to c a l c u l a t e a n a z e o t r o p i c d i s t i l l a t i o n p r o b l e m is
s h o w n a n d d i s c u s s e d , a n d a s a m p l e c o m p u t e r o u t p u t is g i v e n a n d is
briefly discussed. F i n a l l y , c a l c u l a t e d a z e o t r o p i c d i s t i l l a t i o n results are
c o m p a r e d for d e h y d r a t i n g a q u e o u s e t h a n o l f o r t h e three entrainers, n pentane, benzene, a n d d i e t h y l ether.

66
E X T R A C T I V E
Phase
A N D
A Z E O T R O P I C
DISTILLATION
Equilibria
T o c a l c u l a t e p h a s e e q u i l i b r i a s u i t a b l e for m o s t a z e o t r o p i c d i s t i l l a t i o n
p r o b l e m s , the m e t h o d s s h o u l d b e a p p l i c a b l e to three-phase e q u i l i b r i a .
V a p o r - l i q u i d a n d l i q u i d - l i q u i d e q u i l i b r i a are u s u a l l y r e q u i r e d . A suit
a b l e m e t h o d for this p u r p o s e has a l r e a d y b e e n d i s c u s s e d ( 5 ) .
It is a p p l i e d
here to c a l c u l a t e c o m p l e t e l y a l l p h a s e e q u i l i b r i a i n v o l v e d i n the u s u a l
a z e o t r o p i c d i s t i l l a t i o n process.
F r o m E q u a t i o n s 1 a n d 2, the phase e q u i l i b r i a d e p e n d u p o n k n o w i n g
the p u r e c o m p o n e n t v a p o r pressures Pi,
l i q u i d p h a s e a c t i v i t y coefficients
ji a n d i m p e r f e c t i o n - p r e s s u r e coefficients 0 . T h e c o m p u t e r p r o g r a m w h i c h
4
has b e e n d e v e l o p e d uses a n y of f o u r different v a p o r pressure e q u a t i o n s

for p r o v i d i n g .
4
It uses the m o d i f i e d v a n L a a r E q u a t i o n s ( 5 )
to g i v e
l i q u i d phase a c t i v i t y coefficients a n d a M o d i f i e d v a n d e r W a a l s E q u a t i o n
of State (4, 6) to g i v e i m p e r f e c t i o n - p r e s s u r e coefficients 0<.
T h e M o d i f i e d v a n L a a r E q u a t i o n s c a n represent v a p o r - l i q u i d a n d
l i q u i d - l i q u i d e q u i l i b r i a . A c c o r d i n g l y , t h e y c a n b e u s e d to p r e d i c t threephase e q u i l i b r i a w h e n c o n d i t i o n s a l l o w t w o l i q u i d phases as w e l l as a
v a p o r phase to exist. T h i s m i g h t o c c u r o n the trays i n t h e d i s t i l l a t i o n
c o l u m n or at the condenser a n d a c c u m u l a t o r for the o v e r h e a d p r o d u c t
f r o m the a z e o t r o p i c d i s t i l l a t i o n c o l u m n .
F o r e q u i l i b r i u m b e t w e e n phases the fugacities for e a c h c o m p o n e n t
m u s t b e e q u a l i n the s e v e r a l phases. I f the f u g a c i t y coefficient for a n y
c o m p o n e n t i i n a m i x t u r e is d e f i n e d as the r a t i o of t h e fugacity fi o v e r
the v a p o r c o m p o s i t i o n Y a n d the t o t a l pressure P,
4
then
*i-/iVyj?
(3)
If Vi is the l i q u i d m o l a r v o l u m e of p u r e c o m p o n e n t i a n d V} is the p a r t i a l
1
m o l a r v o l u m e of c o m p o n e n t i i n the l i q u i d m i x t u r e , e q u i l i b r i u m b e t w e e n
the l i q u i d a n d v a p o r phases is g i v e n as
ytxPf/Bi-Y?
(4)
and
w h e r e P*
is the reference pressure.
F o r most a z e o t r o p i c d i s t i l l a t i o n p r o b l e m s , the reference pressure is

t a k e n e q u a l to t h e s a t u r a t i o n pressure; a c c o r d i n g l y , the s e c o n d t e r m o n
the r i g h t h a n d side of E q u a t i o n 5 d i s a p p e a r s , to s i m p l i f y the e q u a t i o n to

5.
B L A C K ,
GOLDiNG,
Computer
A N D DITSLER
T h e f u g a c i t y coefficients
67
Calculations
are calculated using a simplified equation
of state d e s c r i b e d earlier (4,6).
F o r this treatment t h e constantsfc*a n d
Oi are c a l c u l a t e d b y k n o w i n g t h e c r i t i c a l t e m p e r a t u r e a n d pressure. T h e
a t t r a c t i o n coefficient & is g i v e n b y g e n e r a l i z e d coefficients f o r n o n p o l a r
substances a n d w i t h t w o other i n d i v i d u a l constants f o r p o l a r substances.
If Yi refers t p t h e v a p o r c o m p o s i t i o n a n d # refers t o b i n a r y v a p o r inter
actions, t h e e q u a t i o n b e c o m e s
log </>i = ( P / 2 . 3 R T )
- o A V R T ] + (P/2.3R T )
2
+ (P/2.3R T ) [27,(1 -
(XGvY,)*-]
[SGW
7,) - 0 . 5 3 * * 7 , 7 * ]
jk
W h e n t h e S's a r e zero, t h e f u g a c i t y coefficients i n t h e m i x t u r e s are c a l c u

l a t e d u s i n g t h e s i m p l e c o m b i n a t i o n rules f o r c o m b i n i n g t h e coefficients
(4,6).
B y u s i n g b i n a r y interactions, t h e equations a r e flexible e n o u g h t o
h a n d l e almost a n y case, e v e n i f s e m i - c h e m i c a l interactions o c c u r i n t h e

v a p o r phase (4, 6).
In azeotropic
d i s t i l l a t i o n , t h e entraner a n d t h e t w o c o m p o n e n t s
b e i n g separated c a n p r o d u c e u n d e r some c o n d i t i o n s three-phase
equi-
l i b r i a . T w o l i q u i d phases m a y b e i n e q u i l i b r i u m w i t h a v a p o r phase. F o r
the three-phase e q u i l i b r i a t h e s o l u b i l i t y o f t h e n o n p o l a r substance i n t h e
p o l a r phase is d e n o t e d b y x, t h e s o l u b i l i t y o f t h e p o l a r substance i n t h e
n o n p o l a r phase b y y, a n d t h e c o r r e s p o n d i n g a c t i v i t y coefficients b y y a n d
, respectively.
T h e relative v o l a t i l i t y f o r c o m p o n e n t s i a n d / is r e l a t e d
to the t o t a l c o m p o s i t i o n X a c c o r d i n g to
f
"
_
li
(y^\
[(y -X )Tj+
i
(Xj-xjyn
\ W [to -
Xi)T< +
/P,flA
( R
(Xi - xjyi]
.
w
O v e r t h e t w o - l i q u i d phase r e g i o n E q u a t i o n 8 gives r e l a t i v e
volatilities
for three-phase e q u i l i b r i a ( 5 ) . I n t h e c o m p o s i t i o n r a n g e w h e r e o n l y a
p o l a r l i q u i d phase a n d a v a p o r phase exists, E q u a t i o n 8 reduces t o
yA0i/y/^*
(9)
a n d w h e r e o n l y a n o n p o l a r l i q u i d phase is i n e q u i l i b r i u m w i t h a v a p o r
phase, E q u a t i o n 8 b e c o m e s
^-rww
(io)
T h e isothermal l i q u i d - l i q u i d equilibria are predicted from the M o d i

fied v a n L a a r E q u a t i o n s b y finding t h e c o m p o s i t i o n s f o r w h i c h t h e a c t i v i
ties a r e e q u a l i n t h e t w o phases f o r e a c h i n d i v i d u a l c o m p o n e n t .
T h i s is
accomplished w i t h a subprogram called S O L T E R .

Either isothermal or isobaric v a p o r - l i q u i d equilibria or both are
calculated w i t h a subprogram
called V L E .
M o d i f i e d v a n L a a r coefficients
f o r t w o o r three temperatures
ForSOLTER
d a t a b y w h i c h l i q u i d phase a c t i v i t y coefficients
and V L E ,
give the
are calculated for both

68
E X T R A C T I V E
programs.
A N D
A Z E O T R O P I C
DISTILLATION
F o r the v a p o r - l i q u i d e q u i l i b r i a , v a p o r pressures of the p u r e
c o m p o n e n t s are c a l c u l a t e d b y one of f o u r different v a p o r pressure e q u a

tions. T h e imperfection-pressure
coefficients
are c a l c u l a t e d a c c o r d i n g
to E q u a t i o n s 6 a n d 7, a s s u m i n g 8s e q u a l to zero. A p p r o x i m a t e values for

the p a r t i a l m o l a r v o l u m e s of the l i q u i d are o b t a i n e d f r o m E q u a t i o n 4
given i n Reference
Azeotropic
(6).
Distillation
Program
ADP/ADPLLE
T h i s t e r n a r y a z e o t r o p i c d i s t i l l a t i o n p r o g r a m uses a s p e c i a l system of
u t i l i t y subroutines w i t h p r o g r a m m e d i n i t i a l i z a t i o n . E i g h t m a i n controls,
K N T R L , are u s e d w i t h v a r i o u s options o n each. F o u r p a r a m e t e r
options
are b u i l t i n t o the p r o g r a m , b u t the values are c h a n g e d b y t h e user b y

u s i n g P R M T R cards.
the pertinent
Twenty-one D A T A
conditions
cards a l l o w the user to g i v e
a n d specifications
for
the
separation
to
be
calculated.
A p r e l i m i n a r y p r i n t o u t , w h i c h prefaces the c a l c u l a t i o n , defines
the
controls K N T R L , the parameters P R M T R w h i c h are a v a i l a b l e , a n d the

DATA
w h i c h must be supplied.
T h i s is f o l l o w e d
by a maximum
of
t w e n t y - o n e V cards w h i c h d e s c r i b e quantities w h i c h are c a l c u l a t e d i m m e

d i a t e l y f r o m the i n p u t d a t a . T h i s completes the p r o g r a m m e d i n i t i a l i z a t i o n
w h i c h describes a n d defines the controls, the parameters, the d a t a , a n d
certain directly calculatable quantities.
A p r i n t o u t t h e n f o l l o w s , g i v i n g the controls a n d parameters
which
h a v e b e e n set a n d the d a t a w h i c h h a v e b e e n s u p p l i e d b y the user o n

cards. A n o p t i o n p r o v i d e s for p r i n t i n g o u t the d a t a , for c a l c u l a t i n g phase
e q u i l i b r i a a n d enthalpies, o r for s u p p r e s s i n g these.
S o m e c a l c u l a t e d re
sults as V quantities are p r i n t e d out next, a n d this is f o l l o w e d b y a stageby-stage p r i n t o u t of m a t e r i a l flows, heat flows, a n d d e t a i l e d phase e q u i
l i b r i u m quantities, Pi /0, x
9
, , 0*. T h e last p r i n t o u t for t h e most
rigorous c a l c u l a t i o n s gives the c o m p o s i t i o n s
of the t w o l i q u i d
phases
f r o m the o v e r h e a d condenser a n d a c c u m u l a t o r a n d the f r a c t i o n of
the
c o n d e n s e d o v e r h e a d w h i c h separates as a n aqueous phase.

T h e p r o g r a m is o p e r a t e d i n three general w a y s .
Simplified calcula
tions are m a d e w i t h the s u b p r o g r a m A D P , w h i c h calculates the a z e o t r o p i c

d i s t i l l a t i o n c o l u m n b u t does not c a l c u l a t e the l i q u i d - l i q u i d e q u i l i b r i a i n
the a c c u m u l a t o r w h e n the o v e r h e a d vapors are c o n d e n s e d .
does t r y via
H o w e v e r , it
a d i a g n o s t i c message to w a r n the user w h e n t w o
phases are e x p e c t e d
o n the trays.
The
liquid
c a l c u l a t i o n s are rigorous
and
r e l i a b l e o n l y w h e n a single l i q u i d phase exists. H o w e v e r , the s u b p r o g r a m

A D P does not m a k e r e l i a b l e c a l c u l a t i o n s w h e n a s e c o n d l i q u i d
appears.
phase
T h i s p r o g r a m is u s e d for o r i e n t a t i o n i n e s t a b l i s h i n g o p e r a t i n g
c o n d i t i o n s for a design.

5.
GOLDiNG,
B L A C K ,
A N D
DITSLER
Computer
69
Calculations
T h e s e c o n d w a y i n w h i c h the p r o g r a m is o p e r a t e d is to c a l c u l a t e
r i g o r o u s l y w i t h the s u b p r o g r a m A D P L L E .
T h e s e c a l c u l a t i o n s are re-
l i a b l e for either t w o - or three-phase e q u i l i b r i a . T h e a z e o t r o p i c d i s t i l l a t i o n

c o l u m n s a n d the l i q u i d - l i q u i d e q u i l i b r i a for the c o n d e n s e d o v e r h e a d i n
the a c c u m u l a t o r is c a l c u l a t e d w i t h this p r o g r a m .
T h e t h i r d w a y that the c o m p u t e r p r o g r a m is o p e r a t e d is to use the
a u t o m a t e d feature.
ADPLLE.
T h i s involves c o m b i n i n g c a l c u l a t i o n s via A D P
and
S t a r t i n g f r o m a set of o p e r a t i n g c o n d i t i o n s , w h i c h m i g h t h a v e
b e e n f o u n d b y u s i n g A D P earlier, the p r o g r a m proceeds
automatically
to find a better set of c o n d i t i o n s . T h e p r o g r a m proceeds w i t h A D P , a n d

after
the
conditions
are established, a
final
c a l c u l a t i o n is m a d e
via
ADPLLE.
I n these c a l c u l a t i o n s the p r o g r a m tries to adjust c o n d i t i o n s so that
o n l y a single l i q u i d phase exists o n a l l of the trays i n the c o l u m n .
The
p r o g r a m first finds the f e e d t r a y l o c a t i o n at a p o i n t w h e r e the r a t i o of

c o m p o n e n t s 2 a n d 3 is the same as the f e e d w h e n c a l c u l a t e d w i t h the
initial operating
conditions.
The
f e e d t r a y is a u t o m a t i c a l l y
displaced
u p w a r d . T h e n the p r o g r a m determines the l o w e s t w a t e r content o b t a i n a b l e i n the e t h a n o l p r o d u c t i f a l l other c o n d i t i o n s except this a n d the

n u m b e r of s t r i p p i n g trays are h e l d constant. U s i n g c o n d i t i o n s a p p r o a c h ing
this l i m i t , a
final
c a l c u l a t i o n is m a d e
with
ADPLLE.
Usually
w h e n i t is c o m p l e t e d , the t o p tray is near s a t u r a t i o n , a n d o n l y a single

l i q u i d phase exists o n the other trays.
F i n a l c a l c u l a t i o n s are m a d e , v a r y i n g the specification for
component
2 i n the o v e r h e a d u n t i l the c o n d i t i o n is f o u n d w h e r e the w a t e r

is satisfied w h e n the entire aqueous phase is r e m o v e d .
proceeds
balance
A s the c a l c u l a t i o n
i n steps of one f u l l tray, often a f r a c t i o n a l t r a y is n e e d e d to
satisfy this exactly, b u t the nearest f u l l tray to satisfying t h e v a l u e is a n

acceptable calculation.
A u s e r s m a n u a l is not r e q u i r e d w i t h this p r o g r a m ; the p r o g r a m is
s u b m i t t e d w i t h o u t a n y d a t a , a n d the user obtains as o u t p u t a d e s c r i p t i o n
of the p r o g r a m s features.
T h i s prefaces the r e g u l a r o u t p u t . It i n c l u d e s
a title a n d i d e n t i f i c a t i o n , a d e s c r i p t i o n of c o n t r o l options K N T R L , i d e n t i fication
of
parameters
PRMTR,
identification
of
data
DATA,
and
d e s c r i p t i o n of d i r e c t l y c a l c u l a t a b l e results, V quantities.
O n a first r u n a l l options m u s t b e set; these are c a r r i e d f o r w a r d as
set or as reset b y the user. T h e r u n o u t p u t shows a c o n t r o l o p t i o n p a r a g r a p h o n l y w h e n options are reset a n d o n l y those that are reset.
Parameters are b u i l t i n a n d r e m a i n fixed unless c h a n g e d b y p a r a m e ter cards. T h e p a r a m e t e r p a r a g r a p h appears o n l y o n r u n s w h e r e resetting
occurs a n d o n l y o n those that are reset.
D a t a values are l o a d e d for a l l d a t a o n a first r u n ; these are c a r r i e d
f o r w a r d u n t i l t h e y are reset.
T h e d a t a p r a g r a p h appears o n a l l runs for

70
E X T R A C T I V E
A N D
A Z E O T R O P I C
DISTILLATION
w h i c h at least one v a l u e w a s reset a n d shows a l l values w h e t h e r reset

or n o t .
B a s i c d a t a decks for phase e q u i l i b r i a a n d enthalpies a r e i n c l u d e d
i n the p r o g r a m itself for t w e n t y different ternaries as s h o w n i n K N T R L 2,
options 1-20. F o r other systems the d a t a are l o a d e d as i n d i c a t e d , K N T R L
2, o p t i o n 2 1 .
T h e L e w i s a n d M a t h e s o n t e c h n i q u e makes tray-to-tray c a l c u l a t i o n s
s t a r t i n g at the b o t t o m a n d c a l c u l a t i n g u p t h e c o l u m n . M a t e r i a l a n d heat
balances are m a d e o n e a c h tray, t h e n u m b e r of trays is d e t e r m i n e d i n t h e
calculations.
Application
A s a m p l e c a l c u l a t i o n is g i v e n s h o w i n g the use of the p r o g r a m to
calculate the azeotropic
d i s t i l l a t i o n of aqueous e t h a n o l mixtures u s i n g
the entraner n-pentane ( K N T R L 2, O p t i o n 7 ) .

T h e f e e d to the c o l u m n is 242.02 m o l e s / h r of aqueous e t h a n o l at a
temperature of 110F. T h e f e e d c o m p o s i t i o n is 85.64 m o l e %
T h e d i s t i l l a t i o n is c a r r i e d o u t at 5 0 p s i a at the reboiler.
ethanol.
T h e pressure
d r o p is a s s u m e d to b e 0.14 p s i p e r tray. T h e v a p o r b o i l - u p at t h e r e b o i l e r
is set at 800 m o l e s / h r . T h e reflux t e m p e r a t u r e is 154.45F. T h e aqueous
phase is s t r i p p e d to r e m o v e d i s s o l v e d entraner a n d r e s i d u a l e t h a n o l . T h e
c a l c u l a t i o n c o n t r o l is set to r e d u c e e t h a n o l i n t h e o v e r h e a d
13.85 m o l e
vapors
to
%.
Another
specification
w h i c h is set at t h e b e g i n n i n g is t h e
f r a c t i o n of entraner w h i c h w i l l b e a l l o w e d
e t h a n o l ; this has b e e n set at 0.62
i n the bottom
mole
product,
10" . A starting a n d m a x i m u m
6
a l l o w a b l e v a l u e for the f r a c t i o n o f w a t e r i n the final b o t t o m p r o d u c t is

set at 2.556
1 0 " . I f the p r o g r a m fails o n the first A D P c y c l e i n t h e

4
a u t o m a t e d c a l c u l a t i o n , t h e v a p o r b o i l - u p is increased.
If a s t r i p p e r is u s e d to r e m o v e entraner a n d r e s i d u a l e t h a n o l f r o m
the aqueous phase, the d a t a i n p u t o n D A T A cards 13, 14 a n d 15 m u s t
b e a p p r o p r i a t e l y specified.
T h e s e d a t a c a r d s g i v e the m o l e fractions of
entraner, e t h a n o l , a n d w a t e r , respectively,
f e r r e d to as D I S T I L L A T E .
i n t h e s t r i p p e r bottoms re-
I f n o s t r i p p e r is i n c l u d e d , the d a t a o f c a r d s
13, 14 a n d 15 c o r r e s p o n d to t h e c o m p o s i t i o n o f the aqueous phase b e i n g

removed.
H e r e the i n p u t is o n l y a first a p p r o x i m a t i o n , a n d t h e p r o g r a m
w i l l c a l c u l a t e a n e w v a l u e i n t h e s e c o n d c y c l e , t h e n u m b e r of w h i c h
m u s t b e specified o r the tolerance g i v e n i f n o s t r i p p e r is i n c l u d e d .
A l t h o u g h t h e rigorous s t r i p p e r c a l c u l a t i o n is m a d e separately, a f a i r l y
r e a l i s t i c b o t t o m p r o d u c t is a s s u m e d w h e n the s t r i p p e r is i n c l u d e d . F o r
this c a l c u l a t i o n a trace o f p e n t a n e 1 1 0 " a n d a s m a l l f r a c t i o n o f e t h a n o l
5
9 1 0 " h a v e b e e n a s s u m e d i n the s t r i p p e r bottoms.

5
T h e accumulator

5.
B L A C K ,
GOLDING,
A N D
DITSLER
Computer
71
Calculations
t e m p e r a t u r e is a s s u m e d the same as the reflux, 154.45F. F o r this s a m p l e

c a l c u l a t i o n n o values are specified o n D A T A cards 7 , 1 2 , 1 8 , 1 9 , 20, a n d 21
since the p r o g r a m does n o t use these for this c a l c u l a t i o n , b u t the
DATA
cards s h o u l d b e i n c l u d e d i n the i n p u t deck.

T h e s a m p l e c a l c u l a t i o n is s h o w n as T a b l e I.
describe the features of the p r o g r a m .
T h e first four pages
T h e first p a g e of the
computer
o u t p u t shows c o n t r o l options K N T R L 1-8; the three w a y s i n w h i c h the

p r o g r a m is u s e d are defined as options 1, 2, a n d 3 for K N T R L 1.
Data
for t w e n t y different ternary systems i n v o l v i n g a n entraner a n d t w o c o m ponents b e i n g separated are i n c l u d e d i n the p r o g r a m ; these
constitute
options 1-20 of K N T R O L 2. O p t i o n 21 is u s e d w h e n a l l d a t a for a n e w

system are u s e d a n d are l o a d e d as i n p u t . T h e t w o options 1 a n d 2 of
K N T R L 3 d e t e r m i n e w h e n the c a l c u l a t i o n s are c o m p l e t e d .
The
options
1 a n d 2 of K N T R L 4 determines the f e e d tray l o c a t i o n ; the K N T R L ' s 5 - 8

a l l o w t h e user to choose reasonable r u n c o n d i t i o n s a n d o u t p u t .
T h e s e c o n d p a g e of c o m p u t e r o u t p u t shows the options for p a r a m e ters w h i c h are w r i t t e n i n t o the p r o g r a m b u t c a n b e c h a n g e d b y p a r a m e t e r
cards P 1 - P 4 .
T h e t h i r d p a g e of c o m p u t e r o u t p u t shows the d a t a i n p u t
as D 1 - D 2 1 w h i c h the user s u p p l i e s i n m a k i n g a r u n . T h e f o u r t h p a g e of
o u t p u t shows t h e t w e n t y - o n e V q u a n t i t i e s w h i c h are c a l c u l a t e d i n the
p r o g r a m f r o m the i n p u t . T h e fifth p a g e s u m m a r i z e s the options
selected
a n d the data i n t r o d u c e d as i n p u t for the s a m p l e p r o b l e m .
thermo-
The
d y n a m i c d a t a are g i v e n o n c o m p u t e r o u t p u t p a g e 6; q u a n t i t i e s c a l c u l a t e d
i n the p r o g r a m f r o m the i n p u t d a t a are s u m m a r i z e d as V quantities o n
o u t p u t p a g e 7. S h o w n o n o u t p u t pages 8 a n d 9 is the final A D P r u n i n
the a u t o m a t e d c a l c u l a t i o n ; these p r o v i d e i n p u t to the A D P L L E r u n . T h e
V quantities are s u m m a r i z e d o n o u t p u t p a g e 10, a n d the final stage-tostage results a p p e a r o n o u t p u t pages 1 1 - 1 5 .
T h e s e last five pages of
computer
output provide
tray-to-tray
s u m m a r y of heat a n d m a t e r i a l flows a n d d e t a i l e d q u a n t i t i e s for the phase

e q u i l i b r i a , also a s u m m a r y of the three-phase condenser a n d a c c u m u l a t o r
results a n d the w a t e r p r o d u c t out. T h e last o u t p u t p a g e s h o w s the fract i o n of the aqueous phase t h a t satisfies the w a t e r b a l a n c e .
Since o n l y
f u l l stages are c a l c u l a t e d , this f r a c t i o n n o r m a l l y is n o t exactly u n i t y , b u t

it s h o u l d reprsent the nearest f u l l stage result to satisfy the w a t e r b a l a n c e .
T h e entraner m a k e u p a n d the w a t e r p r o d u c t out is s h o w n last i n the
computer printout.
F r o m the c o m p u t e r results c o l u m n profiles h a v e b e e n
summarized
a n d are g i v e n i n T a b l e II. T h e pressure profile is l i n e a r w i t h t r a y n u m b e r

r e s u l t i n g f r o m the a s s u m e d i n p u t d a t a for pressure d r o p p e r tray.
i n the table is the t e m p e r a t u r e ,
the f r a c t i o n of p e n t a n e i n t h e
Also
liquid
phase, the f r a c t i o n of w a t e r i n the v a p o r phase o n a pentane-free basis,

a n d the f r a c t i o n of e t h a n o l i n the l i q u i d p h a s e for e a c h t r a y i n the c o l u m n .


a 15
8 16
a 17
3 18
3 19
8 20
S 21
KNTRL
KNTRL
KNTRL
KNTRL
KNTRL
KN RL
KNTRL
KNTRL
1
2
3
1
2
1
2
3
5) 3
5) 3
!>> 3
6) e
6) s
7) 3
KNTRL <
KNTRL (
KNTRL
KNTRL <
KNTRL
KNTRL <
KNTRL
7> 3
7) 3
1
2
4) a
4) a
KNTRL
KNTRL <
KNTRL (
1
2
3) 3
3) 3
<
<
<
KNTRL
KNTRL
KNTRL
<
2)
2)
2)
2>
2)
2)
2)
2) S 13
2) S 14
KNTRL <
K N T R L *<
KNTRL <
KNTRL
KNTRL <
2) s
1
2)
2
3
2) s
4
2) s
S
2) 8
2) g
6
7
2) 3
2) S
9
2) 8
2) 8 3,0
2) 8 11
2) 3 12
KNTRL
KNTRL
1
2
3
PROGRAM
11
i2
SYSTEM
SYSTEM
SYSTEM
PROGRAMS
FROM
CA
CALCULATION ISOBARIC
MOT C A L C U L A T E D
STRIPPER
STRIPPER
STRIPPER
(IF
(lp
(IF
KNTRL(D*2
KNTRL(5)1
KNTRL(D2
2)
3)
3)
OAT
INITIALIZATION AS FOLLOWS
NOT P R E S E N T
( M U S T SET D(2() IF KNTRL(1)2 3)
NOT P R E S E N T
< M U S T S E T 0(2l> IF K N T R L ( 1 > 2 3)
PRESENT f P R O G R A M C Y C L E S OMf.E IF K N T R L U > 2 3)
PRESENT
MOT
PRESENT
CALCULATION
ACCUMULATOR
ISOTHERMAL
UTILITY
PROGRAMMED
C O M P ( 2 ) / C O P ( 3 > *AT10 A S FEEO

CARD INPUT
<D(l2>)
ACCUMULATOR
ACCUMULATOR
MEATER/SUBCOOLER
HEATER/SJBCOOLER
F!.)S f-TFR
IN T O P S VAPOR
IN REFLUX
TRAY AT SAME
T ^ A V 3Y D A T A
SOMTFNT
PNTANj.>ETHMOL-VfATE
-L C O M P O N E N T
C0MP<2>
CMP(3)
SET F E E D
SET F E E O
SET
SET
LO D
S Y S T E M 14
S Y S T E M i5
SYSTEM 1 6
S Y S T E M i7
SySyEM 1 8
13
SY5TEM
SYSTEM
SYSTEM
SYSTEM
4
5
6
7
SYSTEM
SYSTEM
1
2
3
SYSTEM
SYSTEM
SYSTEM
ADPLLE
PROGRAM
C O M B I N A T I O N OF A D P / A O P L L E
ADP
AVAILABLE.
SYSTEM OF UTILITY SUBROUTINES! W J T H
(ADP/ADPLLE)
Ternary Azeotropic Distillation Program ( A D P / A D P L L E )
AZEOTROPIC DISTILLATION PROGRAM
CONTROL OPTIONS ARE
1) 3
1) a
1) 8
KNTRL
KNTRL
KNTRL
KNTRL
KNTRL
TERNARY
PROGRAM USES A SPECIAL
KNTRL
KNTRL
KNTRL
THESE
THIS
Table I.
Computer Output Page 1
to

THROUGH
QUANTITIES
A L L COMPONENT
BUILT
INTO
THE
PROGRAM
THE USE OF PPMTR-CAROS.
ARE
PRINT
DATA
P
NJ
*,0
f,0
3.0
25.0
)
2) -
CMP(3)
FAHRENHEIT
MOLE F R A T I 0 N
MOLES/HR
MOLE F R A CT
TION
MOLE
F R A C I ON
FRACT
F^RENHEH
MOLE
MOLFS/HR
FORM T
FORMAT
FORMAT
FORMAT
FORMAT
FORMAT
FORMAT
FORMAT
< I F KNTRL<3)2>
FORMAT
FORMAT
MOLF
I ON
FRA T
FORMAT
(IF
KNTRL(4)2> FORMAT
FORMAT
ION
FORMAT
I ON
C0MP2)
FORMAT
ION
C0MP(3)
FORMAT
ION
0 M P (
R
(D
I F KNTRL(5)P2> FORMAT
T
(IF
K N T R L ( 5 ) 2 ) FORMAT
DP
(TOP PRESS-AC PRESS) P S H
FORMAT
HFATER/SUBCOOLER TEMP
FAHRENHEIT
FORMAT
NUM E
F C C L E S FOR A L L E
(IF
KNTRL(7)2) FORMAT
REFLUX
C0MP(2)
C0MP2)
V<
V(
8)
5)
6)
3)
1)
2)
V( s
V(
V( 4)V(
V(
V( 7)
V
)s
v(
d o )9
FEED
FEED
BOTTOMS
BOTTOMS
BOTTOMS
BOTTOMS
DISTILLATE
DISTILLATE
FEED
FEED
COMP(1)
C
0MP(2)
(,OMP{
i ))
C0MP(2
C0MP(3)
TOTAL
COMP(l)
C0MP(2)
C0MP(3)
TOUL
MOLES/HR
MOLES/HR
MOLES/HR
MOLES/HR
MOLES/HR
MOLES/HR
MOLES/HR
MOLES/HR
MOLES/HR
MOLES/HR
FORMAT
FORMAT
FORMAT
FORMAT
FORMAT
FORMAT
FORMAT
FORMAT
FORMAT
FORMAT
DESCRIPTIVE IDENTIFICATIONS HAVE BEEN ESTABl 1SHED FOR THESE VARIABLES.
Q(20)
1 )
2)
D( = FEED
I ON
FEED
D< * FEED
TEMPERATURE
(SUBCOOLEO Lieuip)
D< 3) REBOILER
PRESSEE
D( 4)* PRESSURE DROP
PSIA
PER TRAY PSIA
D( 5) REFLUX TEMPERATURE
D( 6)
D< 7)
D( ft) REBOILER VAPOR
D( 9)* BOTTOMS
COMP(l)
D<10> * PTTOMS
MP(3)
( I F KNTRL(3)1)
D<1D s TOPS VAPOR 0cOMP(2)
D(12) * FEED TRAY LOCATION
0(13) r DISTILLATE COMP(l)
MOLE FRACT
D(14) * DISTILLATE
MOLE FRACT
D(15) = DISTILLATE
MOLE FRACT
n<16) FEED
MOLe FRArT
C
*>
0(17) ACCUMULA OR yEMPERATU
f FAHRENHEIT
D(lh)
( I F KNTRL(6)1)
D(19)
( I F KNTRL(7)1)
D(2D TOLERANCE OF C0MP<7> AND CftMPO)
MAY
15,8
15.8
15.8
E15.8
E15.8
15.8
E15.8
15.8
15.8
15.8
E15.8
15.8
E15.8
gl5.8
E15.8
15.8
15.8
15.8
15.8
15.8
E15.8
15.8
ii5.8
E15.8
E15.8
FlO.l
E15.8
Eis.e
E15.8
E15.8
BUT THE VALUES
A T A
PC 3>
Pt 41
Pt
PARAMETERSi
THESE UUAf-iTlTlES ARE TO BE SUPPLIED BY THE USER BY MEANS OF DATACARDS.
AS
SUPPRLKS P R A T I N G OF A L L C M O E T
MAX CYCLESUF KNTRL(1>2#3 AND KNTR^(7)sj.)

MAX CYCLES(JF KNTRL(l)s2.3 AND KNTR.(7),2>
FEED TRAY DISPLACEMENT(ONLY IF KNTRL()=3)
MAXIMUM AQP PASSES ALLOWED (IF KNTRL<1>3>
TMESE
KNTRL ( f t ) * 1
KNTRL < C) s 2
BP
CHANGED
BY
THE
USER
Computer Output Page k
Computer Output Page

D(1C> WHEN KNTFL(1>3
EC
L )
FORMAT
mP
T U
15.8
MOLES/MR
FOR THIS
CALCULATION
(2l)
0(15)
0(16)
D(17>
0(18)
0(19)
0(20)
8!
0( 9 )
0(1C)
0 ( H )
0(12)
o( a)
0( 2 )
0( 3 )
Oi 4 )
D( 5 )
0( 6 )
0< 7 )
0 ( 1>
.00000000
.24202000*03
.85640000*00
,11000000*03
.50000000*02
.14000000*00
,15445000*03
.34999999*01
.80000000*03
,61999999-06
,25560000*03
.13850000*00
.15000000*02
.99999999* 5
,89999999*04
.99990000*00
.00000000
.15445000*03
,00000000
.00000000
.0
SET FEED
A * AT SAME C O M P ( 2 > / C O M P ( 3 > R A T I O S F E E O
ACCUMULATOR CALCULATION ISOTHERMAL
( I F KNTRL<1>23)
HE ATFR/S.jBCOOL N N T P R E S E N T
S T R I P P E R P R E S E N T (PROGRAM C Y C L E S ONCE I F KNTRL*1>2|3>
P R I N T A L L COMPONENT DATA
A P EUSED
COMP(?)
DATA
S E T AS FOLLOWS
C O M B I N A T I O N O F ADP/ADPLLE
PROGRAMS
SYSTEM
7
3NTAN2-ETHNOL-WATER
S T cChP(2) ; C M T K T I N T O P S VAPOR
BEEN
TEST OF AQP/ADPLLE OPTION KNTRL(1>3
OPTIONS HAVE
1)
2)
3)
4>
b)
6)
7)
t)
FOLLOWING
(
(
(
<
<
(
<
(
E C
OF
TERNARY AlEOTROPIC DISTILLATION PROGRAM ( A D P / A D P L L O
VALUE
n FL
h OLE FRACT I ON
COMP(2)
FAHRENHEIT
FEEO TEMPERATURE
(SUBCOOLED L I Q U I D )
PS I A
REBILEP PRESSURE
PSIA
P R E S S U R E DROP P E R TRAY
FAHRENHEIT
REFLUX TEMPERATURE
MOLE F R A C I 3 N
( I F KNTRL(3>2>
REFLUX
OMP<3>
MOLES/HR
R E B I L E P VAPOP
MOLF. F R A C T I
BOTTOMS
COMP(i)
MOLE F R A C T I
BOTTOMS
COMP(3)
(IF KNTRL(3)1)
MOLE F R A C T I
TOPS VAPOR
C0MP(2)
(IF KNTRL<4>2>
F E E D TRAY L O C A T I O N
MOLE FRACTI ON
DISTILLATE
COMPtj)
MOLE FRACTI DN
DISTILLATE
C0NP{2)
MOLE FRACTI ON
DISTILLATE
tOMP<3)
MOLE FRAT1
FEED
COMP(l)
ON
ACC M ,LA OR E M P E R A R E FAHRENHEIJ
<'T F K N T R L ( 5 > 2 >
( I F KNTRL(5)i2>
DP ( T O P P R E S S - A C P R E S S ) PSjA
( I F KMTRL(6)sl)
HEATER/SURCOOLER TEMP
FAHRENHEIT
(IF KNTRL(7)1)
NUMftER OF C Y C L E S F O R A D P L L E
(IF
KNTRL(7)t2)
T O L E A N E OF C < 2 > ANp f.0MP<3)
FE0
FEE"
THE
KNT^L
KNT^L
KNTRL
KNTRL
KNTRL
KNTRL
KNTRL
KNTRL
THE" CONTROL
NO 9 9
RUN
* DISTILLATE cOMP(3>
MOLES/hR
FORMAT 15.8
DISTILLATE TOTAL
MOLES/K&
FORMAT 15.8
* COMP(l) VAPOR-LIOUID FLOW STRIPPING SECTION
MOLES/HR FORMAT 15.8
COMP( ) VAPOR-LIOUID F L O STRIPPING SECTION
MOLES/HR FORMAT
E5,8
COMP<3) VAPOR-LIQUID FLOW STRIPPING SECTION
MOLES/HR FORMAT E15.8
*
H E A FLOW STRIPPING SECTION
/HR FORMAT 15.8
0MP<1) VAP0R-LiQU, OW R I F Y I N G S T i O N MOLES/H* FORMAT 1 5 . 8
* COMPi?) VAPOR-LIQUID FLOW RECTIFYING SECTION MOLES/HR FORMAT 15.8
* COMPt 3 ) yAPOR-LIOUlO FLO RECTlFylNG SECTION MOLES/HR FORMAT
Ei5.8
HEAT FLOW RECTIFYING SECTION

BTU/HR FORMAT 15,8
V(21>
V<11>
V<12)
V(13)
V(i4)
V(15,
V<16)
V<17)
V(18)
( 9)
V(20,
>

DISTI.LATION
PROGRAM
(APP'A3PLLE>
l 2
WATER
WATER
WATER
ETHNOL
ETHNOL
ETHNOL
PN AN2
PNTAN2
PNTAN2
PNT N2
ETHNOL
WATER
100.000
200.000
30000
100.000
200.000
300.000
100.000
200.000
300,000
TEMP
TC
.470300*03
.516300*03
.647000*03
0 C
.13747500-00
22500000*00
.00000000
EPR
,000000
.890000-01
.260000-01
VAP BTU/MOL
,55500+5
,17748900*05
.'20346300*05
.20 37 00+05
,22573300*05
.23969200*05
.19916000*05
.20649000*05
.21290001*05
C4I CC/GM
,141000*03
,759000*02
,247000*02
R?SSURE EQUATIONS
,273160*03 ,525l7o*01
,228980+03 .000000
,273160*03
,404859*01
L I O BTU/ÔL
39682500*04
,82972500*04
.132756 *Q5
.25061000*04
,60349000*04
.10365300*05
.12250000*04
.30270000*04
,48200000*04
PC ATMS
,331000*02
,631000*02
,218000*03
7 CLASSES
COEFFICIENTS FOR VAPOR
.226933*02 ,208645*04
PNTAN2
.816290*01
.162322*04
ETHNOL
.208440*02 ,28i740*04
WATER
AI J
475000*01
.475000*01
oooooo
AMPR
,
oooooo
.0000
.0000
.0000
I
J
PNTAN2-ETHN0L
PNTANs-WATER
ETHNOL-WATER
,159785*01
TEMP
lOOtOOQ
AJI
.82406500-00
2Q3noooo*oi
.39250000-00
.83367725-00
. 77 936* i
,76050000-00
AI J
ciJ
1J
PNTAN2-ETHN0L
PNTAN2-WATER
ETHNOL-WATER
TEMP
87,800
87,800
87.800
CJ
.15507600-00
.25800000-00
.00000000
.87359000-00
.22125185*01
.40080000-00
.88388000-00
.39480000*01
.74600000-00
AJI
PNTAN2-ETHN0L
PNTN2-WATER
EfHNOtATER
.93892120-00
.41365440+01
.72799999-00
AI J
TEMP
75.000 C
75.000 C
75i00Q C
RUN CVCLES - 1
TEMP 154,430 F
CU
.17486900-00
.29700000-00
.00000000
PRESENT
CALCULATION
PRESENT
A JI
.92929000-00
.24165000*01
.40700000-00
STRIPPER
NOT
ACCUMULATOR
HEATER/SUBCOOLER
ISOTHERMAL
MODIFICATION OF PROGRAM TO CALCULATE PHASE EQUILIBRIA B* ?R2f5^?^?2

COEFFICIENTS USED IN iVLE PROGRAM,
USES MODIFIED VAN L*A* COEFFICIENTS
AT 3 TEMPS.
CALCULATES THETAS. GAMMAS AND COMPLETE PHASE EQUILIBRIA AT
EACH STAGE.
AZEOTROPIC

0MP(2)
C0MP(3)
TOTAL
VALUE
COMP(l)
C0MP<3)
TfTAL
COMP(2)
C0MP< >
C0MP(3)
TOTAL
C0MP<1>
COMP(l)
S )
MOLE
WA
PRESSURE^ 49.7 0
TE^P 234.558
VAPOR M/HR
LIO M/HR
LIQ BTU/M
.5139
,5i41
9921,9861
797.7091
1039,7 54
7421.5674
.0024
.0030
3639.4535
798. ?54
2425
77 5 34
F R A C T ON
FTMNOL
WATER
TOTAL
PMTAN2
COMP
KTRAYs 2
KTRAYs J
PRESSURE* 49.860
TElPe 234.74P
CONP
VAPOR M/MR
LlQ M / H R LIQ /
PN AN2
,0558
.0559
9944.2387
FTHNOL
799,1022
1C41.U86
7440.7544
WATER
.O0 3
.00 e
3647.64i7
TOTAL
799,1602
1041,1773
7747273,7
MOI FRACTION V TER (ENTRAINER FREF BASIS)
V<
2 2
M 2
6
VAP BTU/M
18646.5080
2308?,776o
20880.9200
84 97
M
N 5
VAP TU/M
j865.454
23085,5050
088 .670
18448765,0
2
--
KNTRUiOi
VP/THETA
97,9429
49,6905
23,0212
98.421
49,8567
30 0
*NTRL<10 )
VP/THETA
98,3158
49,9997
23,1712
,000003
,000003
Y
,000644
,999353
,000003
,000003
X < 3)
.000494
.999503
.000003
,000003
,000003
11,993293
1,000000
1.11774
.ALPHA
1.000000
11
.OOOOO3
11 9 8 9 7 7 1
,999927
ALPHA
1.116915
1.000000
..ALPHA
11,947562
00007o
,000003
,000003
X ( 2)
000054
,999944
,000007
,999990
,000003
X <01>
,000006
,999992
.000003
.28260159*03
.15005057*03
.24201635*03
.56181042*03
.24201705*03
.40584534-03
.36526080*02
.40580475*02
.40584534*02
.23213671*05
.00000000
VP/THETA
9)
mo>
VUl>
W12)
VUl>
V< 1 )
V<
V( 3 )
V( 4 )
V( 5 )
V( 6 )
V< 7)
VAP BTU/M
18655,6430
23087.8140
20883,2230
18470220,0
MOLES/H
MOLEE/WR
MOLES/HR
OF D(10> ^ H E N KNTPL<1>3
MOLES/HR
MOLES/HP
MOLES/HR
KOLES/HR
MOLES/HR
MOLES/HR
MOLES/HR
MOLES/HR
MOLES/HR
REBOILER
PRESSURE* 50.00C
TEMPt 234.910
C0*P
VAPOR M/HR
L.!0 M/WR
LIS BTU/M
PNTAN2
,0059
,0061 9961,3993
FTHNOL
799.992C
1042.0083
7455.5545
WATER
.0021
.0026
3653.9526
TOTAL
800.0000
1042,0l70
7768820.1
MOLE FACTION A E * <ENTR tNER F ^ E 3 A 1
BOTTOMS
BOTTOMS
DISTILLATE
DlSTiLLAT
DISTILLATE
DISTILLAIE
BOTTOMS
BOTTOMS
FEED
FEED
FEED
FEED
PROGRAM HAS CALCULATED THE FOLLOWING VARIABLES
ENTWALPr EQUATION COEFFICIENTS

VAPOR .335498*02
324675-01 ,125541+05 25974 *02 ,372529-08
'.232640*02 .400800-01 .190630*05 ,199465*02 *.119750*01
.l8l55o*02 -.450000-03 .l909lO*Q5 ,71000*01 .460000-02
PREl IMINAPY RESULTS FOLLOW
LIQUIO
PNTAN2
288600+03
ETHNOL -'.221100*03
WATER -.566000*03
1,000000
2.41380
GAMMA
6,004698
GAMMA
6,70
i,000000
24l0589
6,076075
1,000000
2,410122
GAMMA
. TMTA
1,146209
,999943
,913646
.146420
,999994
983646
THTA
THETA
1,144542
,999999
,983621

<
FREE
BASIS)
PRESSURE*
NATR
V POR M / H R
656.3955
294,4158
.0022
950'8i35
PRESSURE"
WAT R
FREE
B A
>
49,020
3ASIS)
TEMP* 169,194
192835
(ENTRANER F R E E
6^94.4591
4862.3906
2472.8385
7338423
BTU/M
LIQ
=}A lS>
T *p 178,640
656,3956
536.4321
.0028
L I Q M/HR
49.160
( NTRAIN R FR E
49,300
T E M P 211.961
LlQ M / H R
LIQ BTU/M
268,0906
7318,0396
759,9^
52i3.8 5
,0026
2*42,8492
1028,0062
5923958.0
<ENTR IN R
M/HR
268,0904
5i7,8967
,0020
785.9892
VAPOR
FRACTION
(ENTRAINER
KTRAY* s
PRESSURE* 48.880
^ 167.474
LIQ M/HR
L I Q BTU/M
VAPOR M/HR
CO 1
824,6642
6797,2936
824,6641
PNJTAN2
445.87S3
4782.087
203.8620
ETHNOL
.0137
2433,4969
.0131
WATER
1270.5562
7737756.5
1028,5392
TOTAL
MOLE FRA TJ0N WAT R ( NTRAIN R F*E? BASIS)
LIQ M/HR
LIQ BTU/M
COMP
VAPOR M/HR
6817,9567
792.9420
PNTAN2
792,9419
47$9|i707
463.4319
ETHNOL
221.4156
2441.8741
,0056
WAT R
,0050
7630346.8
1256.3795
TOTAL
1014.3625
M0L FRACTION VATER (ENTRAINER FREE BASIS}
KTRAY*
MOLE
0MP
PNT N2
FTWNOL
WATER
TOTAL
KTRAY*
MOLE
PRESSURE
FRACTION
ETHNOL
WATER
TOTAL
BTU/M
9783.6962
7302.4418
3588.4516
7566325.Q
LIQ
: 234.102
PRESSURE* 49.440
TEMP* 231.260
LIQ M/HR
LfQ BTU/M
VAPOR M/MR
39 8n52
0858,5103
39,8050
961.58 >6
6510.6443
719,5733
.0024
,0030
3241,9305
759.3808
1001.3978
6613192.3
FRAC IO
rOMP
PNTAN2
KTRAY*
MOLE
KTRAY* 4
COMP
PNTAN2
ETHNOL
WATER
TOTAL
UAT R
TEMP
PRESSURE* 49.580
LIQ M/HR
V POR M/HR
4.6854
4,6852
1029.8574
787,8411
.0031
.0025
1034.5459
792.5288
ETHNOL
WAT R
TOTAL
MOLE FRACTION
PNTAM2
KTRAY* 3
COMP
" 5
BTU'M
KNTRL'tO
VP/THETA
47 540
13,7553
5,8866
M
2
7
VAP BTU/M
16904,0770
22067,6550
20420,6820
18439207,0
KNTRL(O> 0
VP/THETA
-48,2035
14,3011
6,1290
N 3
54,1901
17,5479
7,5945
KNTRL'(O)VP/
VAP BTU/M
16948,7490
22095,0280
20432.9990
l33l659,0
M 3
17194,0960
22244,0940
20500.1590
7835850
V P
3
Y
,801782
,198205
,000013
,000064
,000031
,000023
.7874
,218201
,000005
,000007
,690351
,309646
,000002
X ( 9)
,649058
.350932
.000011
,000012
X ( 8)
.631133
.360863
,000004
,000005
X ( 7)
.550284
.449714
.000002
,000004
.000003
,341087
,6589|i
,0000
( 6)
VAP
,260787
.739211
,000002
,000003
.000003
78,7405
33,6685
15.609
,052418
947579
,000003
,000003
VP/TH TA
*NTRL'<0 0
,005912
,994085
,000003
,0397o
,960247
.000003
,000003
X ( 4)
,004529
,995468
.000003
BTU/M
*NTRLU0)
VP/THETA
95,0046
47,0586
2.7125
KNTRL(10)
VP/THETA
97,5110
49,3110
22,8338
18059.5690
2275 ,7
20730,5130
16625276,4
Me 3
1856 8360
23035!3850
20859,2590
17314512,0
M 3
VAP BTU/M
N 6
BTU/M
18634,6550
23076,2360
20877,9290
l8267766i0
VAP
M 2
ALPHA
2,364207
1.000000
5.320614
ALPHA
2.926727
1.000000
4,413907
6.319559
1.000000
2.225791
ALPHA
.ALPHA
12,505131
ALPHA
12,158900
1.000000
1,120858
.ALPHA
12.028157
1.000000
1.118356
CAMMA
1,010203
,947050
,959809
TMBTA
TwiTA
1,00*142
.97059
,969674
1,137047
,999859
,981333
THETA
THBTA
,145188
,999483
,913429
GAMMA
1,316007
,909471
23,775542
GAMMA
1,444620
l|663730
17,43143
THETA
,998997
,945259
,960337
THETA
,QQ17_
735
,944806
,939835
2.40460
1.173503
6,035234
GAHM
cAMMA
9,372543
i,004769
2,.751069
GAMMA
6,023060
1,000061
2,446777
6.0826O6
1,000001
2,415163
78
EXTRACTIVE
ro*t
MAC
xoS
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moo
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PRESSURE*
47.480
S )
TEMP* 160,367
A S
COMP(i)
C0MR(2)
C0MP(3)
TOTAL
DISTILLATE
DISTILLATE
C0MP(2)
C0MP(3)
VARIABLES
S E C T ] t ON
S E C T ] ION
STRIPPING SECTION
MOLES/HR
MOLES/HR
MOLES/HR
MOLES/H"
MOLES/HR
VAPOR-LIQUID FLOW STRIPPING

V A P O R - L I Q U I O FLOW STRIPPING
C O M P ( i ) VAPOR-LIQIJIO F L 0
COMP(3)
TOTAL
C0M(2>
MOLES/HR
MOLES/HR
MOLES/HP
MOLES/MR
MOLES/HR
TOTAL
COMP(i)
MOLES/HR
MOLES/HR
C0MP(3)
THE FOLLOWINS
COMP(l)
COMP(2>
CALCULATED
FEED
FEED
HAS
FEED
FEED
BOTTOMS
BOTTOMS
BOTTOMS
BOTTOMS
DISTILLATE
DISTILLATE
PROGRAM
FINAL RESULTS FOLLOW
LIQ
M/wR
LIQ BTU/M
VAPOR M/HR
6244,8645
777,9226
777,9222
432*.1252
130.7335
130.7 99
2207,3051
8,9337
49,5142
917,5858
5443553,7
95,1704
MOLE FRACTION WATER (ENTRAINER FREE BASIS )
KTRAY18
COMP
PNTAN2
ETHNOL
WATER
TOTAL
1
BTU/M
N 5
Vt I t
V( 2)
VI 3 )
V< 4)
Vt 5)
V( 6)
VI 71
V( 8)
V( 9 )
V(10>
vttr>
VU2)
MOLES/HR v t t 3 T
MOLES/HR VC14J
MOLES/HR V<15l
16719.4820
21953.799
20369,4990
16885141,0
VAP
16765 3520
21982,2030
20382,2610
17063895,0
Y
,811883
,3644
,031676
,274701
.063966
,228631
.783370
67097
,049333
I9)
.847792
.142472
,009736
,041106
x ue>
,818033
,174487
,007480
,1072*4
.049112
.00000000
,24202000+03
.405813884-02
.28260159*03
.15005057.03
,24201635*03
,5ei81042-03
.24201705*03
.40584334-03
,36526080*02
.40380475*02
.40384534*02
*.15005057.03
-,242W*35*03
.56181042.03
KNTRK10)
VP/THETA
42,8265
11,7269
4,9839
43 8322
12.2352
5,2050
KNTRL'( io
VP/TMETA
Y
,797334
,180731
.0273
045485
,020595
.187079
,008915
.342798
,007208
X (7
.643332
,339151
,017317
KNTRL<10) 0
M 3
N 5
VAP BTU/M
0MP
KTRAY*17
PRESSURE 47,620
TEMP. 162.i33
COMP
VAPOR M/MR
LIQ M/HR
LIQ BTU/M
PNTAN2
75?,29o5
750,2900
65o3 6753
ETHNOL
160.0411
160.0374
4540.*4524
WATER
47,4410
6,606
2313,8971
TOT L
957,7726
97,0
5622309,8
MOLE FRA TjON WAT R ( NTRAiNF.R F * E E B I
KTRAY=16
Vp/T&Et*
45,0731
trJW
5,4569
13,0792
3,5864
M 3
4
VAP TU/M
16819,1180
22015,40*0
20397,1830
18006621.0
22031.7840
20404,5470
18229770.0
PRESSURE
47.760
TE^P" 164,203
VAPOR M/HR
LIQ M/HR
LIQ
PNTAN2
805,1856
05,1857
6581,6141
ETHNOL
182,4605
424,4768
4604,3625
WATgR
21.9231
21.9236
2345.7019
TOTAL
I00'i569i
1251.5862
7305293.0
MOLE FRACTION WATER (ENTRAINER FRE5 3ASIS)
NEXT TRAY IS FEED TRAY
FTHNOL
191.0646
433.1010
4579,5937
WATER
9,1057
9, 62
2382.9789
TOTAL
1021.4107
1263.4277
7528436.8
MOLE FRACTION WATER (ENTRAINER FREE BASIS)
ALPHA
1.269234
1.000000
,934943
2,471473
1.OOOOOO
5.739363
ALPHA
2.327323
1,000000
5,714574
ALPHA
1.000000
5.695273
94$9
,93942*
TM1TA
THfT*
,994187
,94370
.938201
TgfT*
,991*23
,44073
.939741
,943163
,9*0408
Computer Output Page 1 1
GAMMA
1,100325
3,165983
3,815821
.322906
1,917384
23,876892
GAMMA
.3016*
1,968342
26,369356
GAMMA
1,989408
26,327143

.0023
.0028
3*47,4417
FREE
BASIS)
PRESSURE"
49.580
TE^P 234,%Q2
LlQ M/HR
LQ BTU/M
VAPOR M/HR
4.6852
4.6854
9783.6962
787,8411
1029,8574
7302,448
.0025
,0031
3588,4516
792,5288
1034.5459
7566325.0
(ENTRAINER
COMP
PNTAN2
KtRAY
LQ BTU/M
73l8,o396
*1 211.961
L I Q M/HR
268,0906
49,300
<ENTAIN R F ^ E E ?ASJS)
VAPOR M/HR
268,0904
PRESSURE
49,440
TEMP 231,260
PRESSURE
VAPOR M/HR
LIQ M/HR
LIQ.BTU/M
39 8052
8858 3103
39 8050
961.5896
65lo!6443
7195733
.0030
3241,9305
,0024
759,3808
1001,3978,,
6613192.3
..
TOTAL
MOL F * C i
AE
KfRAY*
4
COMP
PNTAN2
ETHNOL
MOLE FRACTION WATER (ENTRAINER FRE5 3ASIS)
KTRAY*
3
COMP
PNTAN2
ETHNOL
WAT R
TOTAL
WATER
TE^Pf 234,558
PRESSURE" 49,720
LIQ M/HR
LIQ BTU/M
VAPOR M/HR
99 i,986i
.5i39
1039,7254
7421,5674
797,7091
.0030
3639,4535
.0024
7721503,4
1040,2425
798.2254
MOLE FRACTION
TOTAL
WATER
ETHNOL
PNTAN2
COMP
KTRAY*
VAP BTU/M
18655,6430
23087,8140
2Q883.2230
18470220,0
,231020*02
VP/THETA
,98315**02
,499997*02
.231712*02
2
BTU/M
VAP BTU/M
18059.58^0
Mi 3
N 7
VAP BTU/M
18560 83*023035,3850
20859,2591)
7314512.0
M 3
VAP BTU/M
18634,6530
23076,2360
20877,9290
18267766,0
Ml 2
l8646,5n8o
23082,7760
20680,9200
18422972,0
VAP
20882,1670
18448765,0
VP/THETA
,787405*02
950046*02
.470586*02
.217125*02
.493110*02
.226336*02
HE
Vp/T TA
,496905*02
.230212*02"
VP/THETA
.979429+Q2
Me 2
N 5
PRESSURE*
49,860
** 234,748
VAPOR M/HR
LIQ M/HR
L I Q BTU/M VAP BTU/M
VP/THETA
18651.4540
98i42*2
.0558
,0559
9944,2387
.498567*02
799.1022
1041,H86
7440.7544 23085.5050
TOTAL
799,1602
1041,1773
7747273.7
MOLE FRACyI ON wAyER (ENJRAINER FREE 9ASI8)
WATER
KTRAY* 1
COMP
PNTAN2
ETHNOL
REBOILER
PRESSURE
50.000
TEMP* 234,910
COMP
VAPOR M/HR
LIQ M/HR
L I Q BTU/M
PNTAN2
.0059
,QQ61 9961,3993
ETHNOL
799.9920
1042.0083
7455.5545
WATER
.0021
.0026
3653.9526
TOTAL
800,0000
1042,0170
7768820,1
MOLE FRACTION ATER (ENTRAINER FREE 9ASIS)
.10701400*08
.40584534*03
,36526080*02
.40580475*02
144642*
X
.039750
,000003
,341087
.000003
Y
052418
,947579
,000003
,000003
,000003
,000003
000*44
,999353
.000003
,000003
.00592
.994085
.000003
.004529
,995468
,000003
ALPHA
ALPHA
.119476*02
.100000*01
.111692*01
GAMMA
GAMMA
.607608*01
.100000*01
.241012*01
THETA
THETA
.114654*01
.999999-00
.983621-00
GAMMA
.6 47 *01
,100000*01
.241138*01
ALPHA
.425051*02
ALPHA
121590*02
!*01
,112886*01
THETA
113705*01
.995459-00
.981333*00
THTA
GAMMA
.537254*01 .108614*01
GAMMA
,602307*01
.100006*01
.244678*01
4 6
THETA
11 21*01
,999943-00
.983646*00
GAMMA
*
ALPHA
.1202*2*02 .6Q826I*01 ,1459*
.100000*01 .100000*01 .999483-00
,111836*01 ,241516*01 ,983429*00
ALPHA
.l9933*02
,100000*01
.111717*01
,000070 .419698*02 .67*01 .114642*01

,999927 ,100000*01 .100000*01 .999994*00
,000003 ,111699*01 .241059*01 .98364600
X
000*94
,999503
.000003
,000003
.000003
:wm;
.000003
000006
,999992
000003
000003
000002
X
Y
,000007
,999990
,000003
000001
,999997
,000002
L I Q U I D AND VAPOR COMPOSITIONS ARE FOR THE FLOWS FROM THE TRAY
MOLES/HR V U 9 > *
BTU/HR v<20* "
MOLES/HR V(18)
BTU/HR V U 6 >
MOLES/HR v U 7 > *
VAPOR MOLES AND ENTHALPIES ARE FLOWS FROM THE TRAY

LIQUID MOLES A N D ENTHALPIES APE FLOwS TO THE TRAY
HEAT FLOW STRIPPING S Tl| iN

COMP(i) vAPOR-LIQijID FLO> REC-flFylNG S E C ON
C0MP(2) VAPOR-LIQUID FLOW RECTIFYING SECT ON
C0MP<3) VAPOR-LIQUID FLOW RECTIFYING SECT ON
HEAT FLO RECTIF IN6 SECT ON

PRESSUSE* 49.160
TEMP- 178,640
VAPOR M/HR
L I Q M/HR
L Q BTU/M
656.3955
656,3956
6894,4,59i
294,4158
036,4321
4862,3906
.0022
.0028
2472,8385
WATER
PRESSURE
46,980
TE^P 167,474
LIT M/HR
LIQ
BTU/M
24,6642
6797,2936
445.9783
4782.087
.0137
2433.4969
1270.5562
7737756,5
( E N T R A I M R R F*E5 3A5IS)
KTRAYs i l PRESSURE* 48,460

TE^P* 16*.557
CONP
V P0R M/HR
LIO M/HR
LIQ BTU/M
PNTAN2
932.5859
32.5860
6767.7421
ETHNOL
198,2818
440.2982
4757.7173
WAT R
,2240
.2246
2421.5060
.
1031.09i7
1273.1Q97
7730Q85.3
MOLE FRACTION WATER (ENTRAINER FREE B A S I S )
TEMP* 166.766
KTRAYs 1
PRESSURE* 4 8 , 6 0 0
COMP
VAPOR M/HR
LIT M/HR
LIQ BTU/M
832.4717
6777.2436
332.4716
2
440 649
4765.5584
l9R,8485
ETHNOL
2425,3626
,'
,0877
WATER
7743044.8
1273.4248
103.4078
TOT MOLE FRACTION WATER (ENTRAINER FRE IUSIS)
KTRAY=
FRACTION
PRESSURE
VA 0R M/HR
924,6641
203.8620
.0131
102*.5392
48.740
TE^P 167,009
0MP
V A P O R M/HR
LlQ M/HR
L I BTU/M
PNTAN2
631.2025
31226
6786.5001
ETHNOL
199.9386
441.9550
4773.986
WATER
.0341
,0347
2429.1187
TOTAL
1031,1753
1273,9?2
7750579.6
M O L E F R A C T I O N v'ATER ( E N T R A I N E R F R E ? 3ASIS )
MOLE
KTRAYs
CMP
PNT AM2
ETWNOL
WAT^R
TOTAL
COMP
PNTAN2
FTH-NOL
W AT(:R
0 AL
49,020
TE'1P 1 6 9 . 1 9 4
PRESSURE
VA OR M/HH
LIQ M/HR
LIQ BTU/M
792.9419
6*17,9567
792.94?0
4799.1707
221,4156
463,4319
2441,8741
.0056
.0050
7430346.8
1256.37?5
1014.3625
MOLE FRACTION WATER (ENTRAINER F3E" 3ASIS)
KTRAYs
TOTAL
951.8135
1192,*3T5
7133842.3
MOLE FRACTION WATER (ENTRAINER F"*E5 3ASIS)
KtRAY 6
COMP
PNTAN2
ETHNOL
WATER
ETHNOL
517,8967
759,9131
5213,8250
W TER
.0020
,0026
2642,8492
TOTAL
785,9892
1028,3062
5923958,0
MOLE FRAfeTON WATER (ENTRAINER FÊS SASIS)
BTU/M
N" 6
VP/THETA
r+656-13*2
.134698*02
,576065*01
k
BTU/M
N*
22053.0310
20414,1040
18431551,0
V P
! 5*78907*01
.467014*02
VP/THETA
.468633^02
136104*02
* 3822*9*01
VP/THETA
VP/THETA
,*7I540*02
.137553*02
,588661*01
I6880.257o
M*
20415,6010
18444509,0
22056.36oo
16885,6750
M* 2
N* 6
VAP
BTU/M
l689i,99io
22060,2390
20417.3430
18452055,0
VAP
Mi 2
16904,077
22067,6550
20420.6820
1.8439207,0
M* 2
VAP B T U / M
3
N" 3
VAP BTU/M
VP/THETA
16948,7490 . 4 * 2 0 3 5 * 0 2
22095,0280 . 1 4 3 0 1 1 * 0 2
20432.999Q
*429*04
l833659,o
17835185,0
VP/THETA
5l9n*g2
,175479*02
1759T5*i
BTU/M
VAP
N* "3
.536685*02
il*I6-U**02
i7i94.b**0
22244,0940
20500,1590
M 3
22752i8710
20730,5130
6625276.4
GAMMA
THETA
THETA
TH|TA
,0002p0
X
.6537127
.346204
,0000^9
.000078
lg
X
.652849
.347 4
.000027
ALPHA
GAMMA
THETA
,00112e
Y
80748Q
,000441
GMMA
THETA
222373*01 .128557*01 .998403-00

.945640-00
,960670-00
ALPHA
:i & 'Minm $w&
,807122 ,222596*01 .128637*01 .998423-00
.000171
GAMMA
.000031
ALPHA
,8o6o73 .224776*01 .12963*Q1 .998512-00

,193894 ,100000*01 ,197856*01 ,945469-09
,000033 .556344*01 .237304*02 .980537-00
X
.64905*
.350932
.oooojii
,000064
CMMA
,000012
ALPHA
,801762 .236421*04 .131689*01 ,998997-00

.98205 ,100000*01 .l9o947*l ,945259*00
.000013 .532861*01 .237755*02 ,960357-00
,000023
Y
GAMMA
THETA
ALPHA
.781714 ,292673*01 .144463*01 .100173*01
.218281 ,100000*01 ,166373*01 .944806-00
.000005 ,441599*01 ,171431*02 ,959835*00
,000007
ALPHA
63l956*01 .240146*01 .101820*01

100000*01 ,117350+01 ,947050-00
222579*01 ,603523*01 .959809-00
X
.6311-33
.368863
.000004
,000009
X
.55Q284
.449714
.000002
.000003
.69 35i
,309646
.000002
,000004
.000003
,26Q7^7
,739211
,000002
,658911 ,100000*01 .100477*01 .971859-00

,000003 ,123329*01 ,275187*01 ,969674*00
,960247
,000003

14
PRESSURE*
48.040
PRESSURE*
V A P O R M/HR
821.2204
191,0846
9.1057
1021,4107
TEMP*
LlO M / H R
21.2205
433.1010
9.1062
1263.4277
47,900
>
LIQ BTU/M
6672.9946
4679.5937
2382.9789
7528436.8
165.227
MOLE
WAT R
75fi.29 5
160,0411
47,4410
957.7726
PRESSURE
V A P O R M/HR
FRACTION
ETHNOL
WATER
TOT
0MP
PNTAN2
KTRfiY* 1 7
( N T R A I N R FRE
TE^P*
M/HR
75O.29Q0
60.0374
6,8606
917.89Q
LiQ
47,620
B
3ASI8)
4540.4524
2313.8971
5622309.8
65o3,8753
LQ
162,133
KTRAY* 1 6 PRESSURE
47.760
TEMP* 1 6 4 . 2 0 3
COMP
VAPOR M/HR
L I Q M/HR
L I Q BTU/M
2
8 0 51856
8Q5 1857
6581,6141
ETHNOL
182'.4605
424,4768
4604.3625
WATER
21.9231
21.9?36
2345.7019
TOJAL
1009.5691
1251.5862
7305293.0
M O L E F R A C T I O N WATER ( E N T R A I N E R F R E 5 3 A S I S )
NEXT TRAY IS FEED TRAY
165.766
MOLE FRAC i0N wAyER (ENyRAINER FREE BASIS)
KTRAY* 1 5
COMP
PNTAN2
ETHNOL
WATER
TOTAL
LIQ B
6742,1831
4736.6308
2411.1252
7685310.7
166,097
L T Q BTU/M
6718,2870
4716,9242
2401.4117
763435Q.7
BASIS)
TE^P*
L I Q M/HR
V A P O R M/HR
COMP
828,2290
92.22B8
2
436,99&8
194,9825
THNOL
3.65*4
3.6558
WATER
1026.8671
1269.8842
TOTAL
MOLE F R A C T I O N
WATER ( E N T R A I N E R F R E E
KTRAY*
TE P
48 1 8 0
KTRAY* 1 3
PRESSURE
0MP
V A P O R M/HR
L I Q M/HR
3 L 1 0 0 6
PNT AN2
31.100*
196,7734
ETHNOL
438,7897
1,4478
1.4493
WATER
1271,3308
1
0
29,3218
TOTAL
M O L E F R A Q T I ON W A T R ( J T N T R A I N E R F & E E
48,320
TEMP* 1 6 6 , 3 4 3
PRESSURE*
KTRAY* 1 2
V A P O R M/HR
L I Q M/HR
L I Q BTU/M
COUP
332,2150
832.2152
PNTAM2
6756,8310
439.7081
197,6918
ETWNOL
4748,7144
.5708
.5703
WAT R
2417.0756
1272.4941
1030.4771
TOTAL
77i2565.2
MOLE F R A C T I O N ' M A T E R ( E N T R A I N E R F R E E B A S I S )
N 6
3
BTU/M
* 4
,450731+02
,127925+02
,545688+01
VP/THETA
VP/THETA
.457047*02
.130792+02
,558635*01
M 3
N* 5
VP/THFTA
V A P TU/M
16765,3520 .438322+Q2
21982,2030 .122352+02
20382,2610 ,520498+01
17063895,0
ll8o
VAP BTU/M
1.6819
2 2 0 1 5 * . 40*0
20397,1830
18006621.0
Ma 3
16845.7060
22031.7840
20404.5470
18229770,0
VAP
M*
VP/THETA
,460426*02
.132332*02
.565557*01
V A P BTU/M
VP/THETA
462556*TJ2
,133303*02
,5699*0l
16859,718
22040,4060
20408.4250
1.8335807.0
Ms 2
V A P gTU/M
16868,30?0
22045,6850
20410,7990
18386810.0
Ma 2
VP/THETA
,464180*02
,134043*02
,573175*01
N *
BTU/M
VAP
16874,6930
22049,6130
20412.5660
l84i4Q4liO
Ma 2
GAMMA
THETA
THETA
THETA
THETA
GAMMA
^HPTA
,228651
ALPHA
,049112
,78337 .247i47*oi ,l3229l*oi .994il7*oo

,167097 ,100000+01 .191758*01 ,941578*00.
,049533 ,573936*01 .2387Q9*02 ,93620400
X
.43332
,339151
.017517
,107264
GAMMA
,020593
ALPHA
797554 232732*01 ,130017+01 99*623*00

,180731 ,100000*01 .196836+01 .944075*00
,021715 .571457+01 .2*3*94+02 .959741*00
X
.649994
,342798
,007208
,045485
GAMMA
,008298
ALPHA
,804006 .226759+01 .129094+01 ,997709-00

,187079 .100000+01 .198941+01 .945163*00
,008915 ,569528+01 .265271+02 ,9*0408*00
X
,652722
.344396
.002882
,018404
.003290
GAMMA
_ ,998133-00
,806559 ,224263*01 ,128732+01
,189881 ,100000*01 199722+01 ,94557000
,003360 .568041*01 ,2*5457+02 ,960652*00
ALPHA
Page l A
X
.653721
.345140
,001139
Y
Computer Output
,007304
ALPHA
.001296
,8 7425 .223160+01 .128596*01 .998324-00

.9168 ,100000*01 ,199956*01 ,945688*00
,001407 ,566762*01 .265084*02 .960717*00
,002876
Y
ALPHA
GAMMA
THfTA
8076Q2 .222620*01 .126551*01 ,998385*00
,191845 .100000*01 .199964*01 ,945688*00
,000553 ,565548*01 ,264472*02 .960708*00
X
654003
,345548
.000449
,000510
,653979
,345845
,000176

AND HEATER OR SU3C00LER
5
BTU/M
CALCULATIONS
16719,4820
21953.7990
20369,4990
I6883l4li0
VAP
.041106
,818033
,174487
,007460
CYCLE NO 1
VP/THETA
,428265*02
.117269*62
,498386*01
,274701
CONDENSER
TOTAL HFAT
HEAT LOAD
COMP
PNTAN2
ETHNOL
WATER
0 AL
PRODUCT OUT
PRODUCT M/HR
.0004
.0037
40.5805
40.5845
ENTRAINER MAKE-UP .40584534-03 M/UR
FRACTION OF AQUEOUS PHASE TO SATISFY WATER BALANCE ,956^1*22-00
NO HEATER OR SUBCOOLER
FRACTION OF AQUEOUS PHASE .059107

,55574808*07 BTU/HR
,11327660+08 BTU/HR
VAPOR-LIQUID EQUILIBRIA FOR AQUEOUS PHASE

PRESSURE" 44,814
TEMP" 154.450
COMP
ALPHA
GAMMA
THETA
VP/THETA
PNTAN2 ,001251 ,808692 .646451*03 ,148266*04 ,737158*03 ,98874-00 ,39300*02
ETHNOL .249871 .108946 .436007-00 .100000*01 , l 9 n 4 i * o i ,94295-00 .10222*02
WATER
,748878 ,082363 .109981*00 ,252247-00 ,114030*01 ,95940-00 ,43223*01
THETA
GAMMA
Y
ALPHA
,811883 .126923+01 .10033+01 ,991243*00
,136441 .100000*01 .36598+01 ,943219*00
,051676 .883494+01 .65858+02 ,959426*00
VAPOR-LIQUIO EQUILIBRIA FOR ORGANIC PHASE

PRESSURE- 44,815
TEMP* 154,450
COMP
ALPHA
GAMMA
THETA
VP/THETA
PNTAN2 .876890 .C8694 .922230-00 .975464*00 ,105166+01 ,98874-00 ,39300*02
ETHNOL .115232 .108944 .945427-00 .100000*01 .414479*01 ,94295-00 ,10222*02
WATER
.007878 .082362 .104550-02 .110584*02 ,108402*03 ,95940-00 ,43223*01
ACCUMULATOR
ACCUMULATOR
,480
TEMP* 160.367
PRESSURE
L I Q M/HR
L I Q BTU/M
VAPOR M/HR
777,9222
6244.8645
777,9226
130.7299
4328,252
130.7335
ETHNOL
8,9337
2207.3051
49,5142
WATER
9!7.5858
5443553.7
958.1704
TOTAL
MOLE FRACTION WATER (ENTRAINER FREE BASIS)
KTRAYs
COMP
84
E X T R A C T I V E
Table II.
A N D
A Z E O T R O P I C
DISTILLATION
Column Profiles in Azeotropic Distillation

Dehydration
of Aqueous
Ethanol
Using n-Pentane as Entraner
Tray No.
(Equil.)
18
17
16"
15
14
13
12
11
10
9
8
7
6
5
4
3
2
1
Reboiler
t, F
160.37
162.13
164.20
165.23
165.77
166.10
166.34
166.56
166.77
167.01
167.47
169.19
178.64
211.96
231.26
234.10
234.56
234.75
234.91
Pressure,
psia
Fraction
Pentane
in Liquid
Fraction
Water in Vapor
(Pentane-Free)
Fraction
Ethanol
in Liquid
47.48
47.62
47.76
47.90
48.04
48.18
48.32
48.46
48.60
48.74
48.88
49.02
49.16
49.30
49.44
49.58
49.72
49.86
50.00
0.818
0.643
0.650
0.653
0.654
0.654
0.654
0.654
0.653
0.649
0.631
0.550
0.261
0.040
0.0045
0.00049
0.00005
0.000006
0.000001
0.275
0.229
0.107
0.045
0.018
0.0073
0.0029
0.0011
0.00044
0.00017
0.000064
0.000023
0.000007
0.000004
0.000003
0.000003
0.000003
0.000003
0.000003
0.175
0.339
0.343
0.344
0.345
0.346
0.346
0.346
0.347
0.351
0.369
0.450
0.739
0.960
0.996
0.9995
0.99994
0.999992
0.999997
B o t t o m Product, M o l e fraction ethanol

M o l e fraction water
M o l e f r a c t i o n pentane =
0.99999706
0.00000232
0.00000062
Stripped Water Product, M o l e fraction water

=
M o l e fraction ethanol =
M o l e f r a c t i o n pentane =
0.99999
0.000009
0.000001
Feed, 8 5 . 6 4 % m ethanol, 14.36%m water

a
Tray No. 16 is the feed tray.
T h e t e m p e r a t u r e profile is most c l e a r l y seen i n F i g u r e 1. T h e t e m p e r a t u r e changes s l i g h t l y f r o m the r e b o i l e r u p a f e w trays; t h e n i t drops

r a p i d l y for a b o u t three trays.
A f t e r this it d r o p s o n l y five degrees i n
the next n i n e trays a n d s l o w l y drops another f o u r degrees f r o m the f e e d

to the t o p tray.
T h e b e h a v i o r of the t e m p e r a t u r e profile is e x p l a i n e d w h e n the c o m p o s i t i o n profiles of F i g u r e 2 are e x a m i n e d . I n the first f e w trays n e a r the
r e b o i l e r , the c o n c e n t r a t i o n of e t h a n o l i n the l i q u i d is h i g h , a b o v e 99
m o l e % . F r o m tray 4 to tray 7 the e t h a n o l c o n c e n t r a t i o n d r o p s
99.6-45.0 m o l e
%.
In
this
same
region
the
pentane
from
concentration
increases f r o m a p p r o x i m a t e l y 0.5-55.0 m o l e % . T h e w a t e r c o n c e n t r a t i o n ,

GOLDiNG,
B L A C K ,
160
Figure 1.
Computer Calculations
A N D DITSLER
200
TEMPERATURE, F
240
Temperature profile for 50 psia column dehydration of

aqueous ethanol using n-pentane
n-pentane-to-ethanol ratio 3.22 (mole basis)
20
TOP
ENTRAINER
"IN LIQUID
FEED 16
><
/WATER IN
VAPOR
12 (ENTRAIN
ER FREE)
8
ETHANOL
IN LIQUID
4
0
0
Figure
20
40
60
MOLE, %
80
2. Composition profiles in 50 psia column

dration of aqueous ethanol using n-pentane
100
dehy

86
E X T R A C T I V E
A N D
A Z E O T R O P I C
DISTILLATION
100
TRAYS
Figure
3.
Relative
volatility profiles in 50 psia column

aqueous ethanol using n-pentane
dehydration
of
w h i c h is l o w , begins to increase. F r o m t r a y 8 t o t r a y 17 w a t e r c o n t i n u e s to
b u i l d u p i n the v a p o r o n a pentane-free basis. O v e r this r e g i o n the c o n c e n t r a t i o n o f p e n t a n e i n t h e l i q u i d is n e a r l y constant w h i l e the e t h a n o l
c o n c e n t r a t i o n decreases s l o w l y .
O n the t o p t w o trays p e n t a n e increases
a n d e t h a n o l decreases i n the l i q u i d w h i l e w a t e r continues to b u i l d u p i n

the v a p o r .
F i g u r e 3 gives the r e l a t i v e v o l a t i l i t y profiles also for the s a m p l e c o l u m n c a l c u l a t i o n ; these c o r r e s p o n d to the t e m p e r a t u r e a n d c o m p o s i t i o n
profiles of F i g u r e s 1 a n d 2.
Pentane is easily s e p a r a t e d f r o m
ethanol
w h i l e w a t e r is not as r e a d i l y separated i n the b o t t o m of the c o l u m n ,

r e b o i l e r to t r a y 5.
T h e p e n t a n e v o l a t i l i t y decreases a n d that of
water
increases r a p i d l y , r e l a t i v e to ethanol, o n p r o c e e d i n g f r o m tray 5 to 8.

T h e y r e m a i n n e a r l y constant for the next n i n e trays w h e r e the s e p a r a t i o n
of w a t e r r e l a t i v e to e t h a n o l is f a v o r a b l e ; t h e s e p a r a t i o n of p e n t a n e relative
to e t h a n o l is s t i l l f a v o r a b l e i n this r e g i o n . O n the t o p t r a y c o n d i t i o n s are
f a v o r a b l e for s e p a r a t i n g w a t e r , b u t for s e p a r a t i n g p e n t a n e t h e y are less
favorable.
It becomes difficult to r e m o v e e t h a n o l f r o m the t o p p r o d u c t .
For
t h e c o n d i t i o n s o f this s a m p l e c a l c u l a t i o n , t h e r e d u c t i o n of e t h a n o l i n the
o v e r h e a d vapors b e l o w a b o u t 13.5 m o l e % is a c c o m p a n i e d b y a b u i l d i n g

5.
B L A C K ,
GOLDING,
A N D
DITSLER
Computer
87
Calcuhtions
u p of w a t e r i n t h e o v e r h e a d vapors a n d a t e n d e n c y to f o r m a s e c o n d l i q u i d
phase i n the top of the c o l u m n .
T h e effect o n tray r e q u i r e m e n t s of c h a n g i n g the n-pentane-to-ethanol
r a t i o is s h o w n i n F i g u r e 4. T h e w a t e r content of the b o t t o m p r o d u c t ,
e t h a n o l , is s h o w n vs. this r a t i o i n F i g u r e 5. W i t h n-pentane as entraner
the w a t e r content of the e t h a n o l p r o d u c t is r e d u c e d b e l o w ten p p m , o n
a m o l e basis.
Comparison of Entrainers
T h e c h o i c e of a n entraner u s e d to m a k e a d e s i r e d separation i n a n
a z e o t r o p i c d i s t i l l a t i o n d e p e n d s o n the b i n a r y m i x t u r e b e i n g separated a n d
the n o n i d e a l i t i e s of these c o m p o n e n t s w i t h the a d d e d entraner.
several different
final
While
entrainers m i g h t b e u s e d to p r o v i d e a separation, the
selection m a y d e p e n d o n the r e q u i r e d p u r i t y of the p r o d u c t .
several entrainers c a n p r o d u c e a p r o d u c t of d e s i r e d p u r i t y , the
If
final
c h o i c e m a y d e p e n d o n a n e c o n o m i c e v a l u a t i o n of the several schemes.

F o r the a z e o t r o p i c
d e h y d r a t i o n of aqueous e t h a n o l m i x t u r e s a p -
p r o a c h i n g the constant b o i l i n g m i x t u r e , a b r i e f c o m p a r i s o n is s h o w n for

the entrainers, n-pentane, benzene, a n d d i e t h y l ether. S i n c e w a t e r is most
n o n - i d e a l i n n-pentane, the driest e t h a n o l is e x p e c t e d to b e p r o d u c e d i f
n-pentane is u s e d .
12
16
20
TRAYS
Figure
4.
Effect of changing the n-pentane-to-ethanol

basis) on trays required
ratio (mole

E X T R A C T I V E
^1
0
A N D
A Z E O T R O P I C
DISTILLATION
I
I
2
4
6
MOLE FRACTION WATER IN BOTTOM PRODUCT, 10
1
5. Fraction
Figure
water in bottom product ethanol vs.

to-ethanol ratio (mole basis)
n-pentane-
DIETHYL ETHER
135 psia
\ BENZENE
\
14.7 psia
" \
PENTANE
50 psia
,
I
L
1
40
80
120
MOLE FRACTION WATER IN BOTTOM PRODUCT, 10
LZ
Figure
6. Comparing entrainers, n-pentane, benzene,

ether, for water content of ethanol product
and diethyl

5.
B L A C K ,
GOLDiNG,
A N D
DITSLER
Computer
89
Calculations
C a l c u l a t i o n s h a v e b e e n m a d e u s i n g the a u t o m a t e d feature o f the

A z e o t r o p i c D i s t i l l a t i o n P r o g r a m A D P / A D P L L E . T h e same m o l e fract i o n o f entraner i n the e t h a n o l p r o d u c t , 0.62 1 0
c a l c u l a t i o n s i n v o l v i n g e a c h entraner.
- 6
has b e e n u s e d i n
U s i n g n-pentane, the
azeotropic
d i s t i l l a t i o n w a s c a l c u l a t e d for a c o l u m n w i t h a r e b o i l e r at 50 p s i a .
The
c o r r e s p o n d i n g pressures w e r e 14.7 p s i a a n d 135 p s i a for cases i n v o l v i n g

b e n z e n e a n d d i e t h y l ether, r e s p e c t i v e l y . C a l c u l a t i o n s w e r e m a d e also at
h i g h e r pressures for cases u s i n g n-pentane a n d benzene.
A l t h o u g h the
a b o v e pressures are n o t necessarily the o p t i m u m for e a c h solvent, c o m parisons h a v e b e e n m a d e for the three cases as i n d i c a t e d .
MILLIONS BTU/UNIT TIME

Figure
7. Comparing the entrainers, n-pentane, benzene, and diethyl ether,

for reboiler and condenser loads in dehydrating aqueous ethanol
Condenser loads, heat removed, btu/unit time
Reboiler loads, heat added, btu/unit time
T h e c a l c u l a t e d results, c o m p a r i n g t h e w a t e r content o f the e t h a n o l

p r o d u c t for the entrainers, n-pentane, b e n z e n e , a n d d i e t h y l ether, are
s h o w n i n F i g u r e 6. T h e m o l e f r a c t i o n w a t e r i n the e t h a n o l p r o d u c t i s
p l o t t e d vs. t h e e n t r a i n e r - t o - e t h a n o l r a t i o , o n a m o l e basis. n - P e n t a n e p r o duces e t h a n o l o f lowest w a t e r content; b e n z e n e comes next, a n d d i e t h y l
ether comes last. E n t r a i n e r - t o - e t h a n o l ratios o f 2.5-3.5, m o l e basis, are
a d e q u a t e w h e n n-pentane o r b e n z e n e is u s e d ; for d i e t h y l ether, the r a t i o
m u s t b e a b o v e four.
C o n d e n s e r a n d r e b o i l e r loads are c o m p a r e d for the same three e n trainers i n F i g u r e 7. F o r d i e t h y l ether-to-ethanol ratios o f a b o u t 4.2, the

90
E X T R A C T I V E
A N D
A Z E O T R O P I C
DISTILLATION
DEE
135 p s ^ a ^ ^ ^ ^
PENTANE
/
50 psia
/
BENZENE
14.7 psia
'
1
1
1
1
16
24
32
40
MAXIMUM FLOW IN COLUMN, IN MOLES, 10"
2
Figure 8. Comparison of maximum flows on any tray for entrainers, n-pentane,

benzene, and diethyl ether, in dehydrating aqueous ethanol by azeotropic
distillation
DLETHYL\
1
!^ 3
ETHER
^ 135 psia
BENZENE
\ 14.7 psia
\N-PENTANE
L _
50 psia
20
TRAYS,
40
1
60
EQUILIBRIUM
Figure 9. Comparing tray requirements for the entrainers, n-pen

tane, benzene, and diethyl ether, in dehydrating aqueous ethanol by
azeotropic distillation

5.
B L A C K ,
GOLDiNG,
A N D
DITSLER
Computer
91
Calculations
condenser a n d r e b o i l e r loads c o m p a r e f a v o r a b l y w i t h those for
benzene-
to-ethanol ratios of a b o u t 3, m o l e basis. A t the h i g h e r r a t i o , heat loads

w i t h n-pentane are a b o u t 8 0 % of those for d i e t h y l ether. A t the l o w r a t i o
of a b o u t 3, the heat loads w i t h n-pentane are o n l y 6 0 % of those
for
benzene.
T h e m a x i m u m flow o n a n y t r a y i n the c o l u m n is c o m p a r e d for the
three entrainers, n-pentane, benzene, a n d d i e t h y l ether, i n F i g u r e 8.
At
the h i g h entrainer-to-ethanol r a t i o of 4.2, the m a x i m u m flow w h e n n pentane is u s e d is a b o u t 7 0 % of that for the case u s i n g d i e t h y l ether.
F o r the l o w ratio of a b o u t 3, the flows w i t h n-pentane are a b o u t 7 5 % of
those u s i n g benzene.
A s m a l l e r d i a m e t e r c o l u m n is r e q u i r e d w i t h n -
p e n t a n e t h a n w i t h either of the other entrainers.

T o t a l tray r e q u i r e m e n t s for the three entrainers are c o m p a r e d i n
F i g u r e 9. T h e least n u m b e r of trays is r e q u i r e d w h e n n-pentane is u s e d ;
the most are r e q u i r e d w h e n d i e t h y l ether is the entraner. If b e n z e n e is
u s e d as entraner at h i g h e r pressure t h a n 14.7 p s i a , the c o r r e s p o n d i n g
c u r v e i n F i g u r e 9 is shifted to the r i g h t , m o r e trays b e i n g r e q u i r e d .
The
c o m p u t e r p r o g r a m for
azeotropic
distillation A D P / A D P L L E
makes possible not o n l y a c o m p a r i s o n of entrainers for a separation b u t

also gives results of a q u a l i t y r e q u i r e d for a c t u a l d e s i g n c a l c u l a t i o n s .
Acknowledgment
S o m e of the u t i l i t y subroutines d e s c r i b e d here w e r e d e s i g n e d
after
a g e n e r a l system of u t i l i t y - s u b r o u t i n e p r o g r a m m i n g d e v e l o p e d b y H . W .
B r o u g h of S h e l l C h e m i c a l C o m p a n y .
W e also w i s h to a c k n o w l e d g e
s u p p o r t of E . G . F o s t e r a n d L . J . T i c h a c e k i n f a c i l i t a t i n g this w o r k .
List
of
Symbols
OLi
v a n der W a a l s a t t r a c t i o n constant for c o m p o n e n t i
bi
v a n der W a a l s c o v o l u m e for c o m p o n e n t i
fi
f u g a c i t y of c o m p o n e n t i i n vapor-phase m i x t u r e
0.5
P*
Pi
w
w

the
92
E X T R A C T I V E
A N D AZEOTROPIC
DISTILLATION
Xi
t o t a l l i q u i d c o m p o s i t i o n i n r e g i o n o f t w o l i q u i d phases
Xi
l i q u i d c o m p o s i t i o n , m o l e f r a c t i o n , p o l a r phase
tji
l i q u i d c o m p o s i t i o n , m o l e f r a c t i o n , n o n p o l a r phase
Yi
vapor composition, mole fraction component i
an
v o l a t i l i t y o f c o m p o n e n t i relative to c o m p o n e n t /
ji
l i q u i d - p h a s e a c t i v i t y coefficient, p o l a r p h a s e
Yi
l i q u i d - p h a s e a c t i v i t y coefficient, n o n p o l a r phase
&a
b i n a r y v a p o r i n t e r a c t i o n coefficient
6i
imperfection-pressure
n o n p o l a r p a r t o f the m o l e c u l a r attractive coefficient at zero

pressure
p o l a r p a r t o f the m o l e c u l a r a t t r a c t i o n coefficient at zero pressure

$
+ > the l i m i t i n g v a l u e o f the m o l e c u l a r a t t r a c t i o n coefficient
at zero pressure
<f>i
f u g a c i t y coefficient f o r c o m p o n e n t i at saturation pressure Pi
fugacity coefficient f o r c o m p o n e n t i i n a v a p o r pressure
coefficient
Literature Cited
1. Gerster, J. ., Chem. Eng. Progr. (1969) 65 (9), 43.
1964.
3. Robinson, C. S., Gilliland, E. R., "Elements of Fractional Distillation,"
p. 312, McGraw-Hill, New York, 1950.
4. Black, C., Ind. Eng. Chem. (1958) 50, 391.
6. Black, C., A.I.Ch.E. J. (1959) 5 (2), 251.
8. Black, C., Derr, E. L., Papadopoulos, M. N., Ind. Eng. Chem. (1963) 55
(9), 38.
9. Null, H. R., Palmer, D. ., Chem. Eng. Progr. (1969.) 65 (9), 47.
10. Yamada, I., S. Hidezumi, A. Kanji Kagaku Kogaku (1967) 31, 395-398.
11. Berg, L., Chem. Eng. Progr. (1969) 65, (9), 53.

6
Prediction of Isobaric Vapor-Liquid
Equilibrium Data for Mixtures of Water
and Simple Alcohols
A. ANDIAPPAN and A. Y. McLEAN
Annamalainagas University, Tamifnedu, India and Nova Scotia Technical
College, Halifax, Nova Scotia
The Non-Random, Two Liquid Equation was used in an

attempt to develop a method for predicting isobaric vapor
liquid equilibrium data for multicomponent systems of water
and simple alcoholsi.e., ethanol, 1-propanol, 2-methyl-1propanol (2-butanol), and 3-methyl-1-butanol (isoamyl alcohol). Methods were developed to obtain binary equilibrium
data indirectly from boiling point measurements. The binary
data were used in the Non-Random, Two Liquid Equation to
predict vapor-liquid equilibrium data for the ternary mixtures, water-ethanol-1-propanol, waterethanol-2-methyl1-propanol, and water-ethanol-3-methyl-1-butanol. Equilibrium data for these systems are reported.
T p h e d e s i g n of a z e o t r o p i c o r extractive d i s t i l l a t i o n c o l u m n s , as w i t h c o n A
v e n t i o n a l c o l u m n s , d e m a n d s a k n o w l e d g e of the v a p o r - l i q u i d e q u i l i b -
r i u m p r o p e r t i e s o f the system to b e d i s t i l l e d . S u c h k n o w l e d g e is o b t a i n e d
e x p e r i m e n t a l l y o r c a l c u l a t e d f r o m o t h e r properties of the c o m p o n e n t s o f
the system.
S i n c e the systems i n a z e o t r o p i c o r e x t r a c t i v e d i s t i l l a t i o n
processes h a v e at least three c o m p o n e n t s , d i r e c t m e a s u r e m e n t
of t h e
e q u i l i b r i u m p r o p e r t i e s is l a b o r i o u s a n d , therefore, expensive, so m e t h o d s
of c a l c u l a t i o n o f these d a t a are d e s i r a b l e .
F o r a z e o t r o p i c d i s t i l l a t i o n e s p e c i a l l y the systems are n o n - i d e a l w h i c h
makes c a l c u l a t i n g v a p o r - l i q u i d e q u i l i b r i u m p r o p e r t i e s m o r e difficult t h a n ,
for e x a m p l e , i n d i s t i l l a t i o n of m i x t u r e s of s i m p l e h y d r o c a r b o n s . W o r k p r e d i c t i n g the v a p o r - l i q u i d e q u i l i b r i u m properties of t e r n a r y m i x t u r e s o f
93
94
E X T R A C T I V E
A N D
A Z E O T R O P I C
DISTILLATION
water, e t h a n o l , a n d o n e of the s i m p l e alcoholsi.e., 1-propanol, 2 - m e t h y l 1-propanol, 3 - m e t h y l - l - b u t a n o l , ( a l l f o r m b i n a r y azeotropes w i t h w a t e r )

i s p r e s e n t e d here.
A q u e o u s solutions of these alcohols o c c u r w h e n sugar solutions are
fermented
a n d m a y b e separated b y d i s t i l l i n g t h e m i x t u r e s .
It is a
c o m m o n , e c o n o m i c a l l y v a l u a b l e process for m a n u f a c t u r i n g p o t a b l e l i q u o r s
a n d for p r o d u c i n g i n d u s t r i a l a l c o h o l f r o m f e r m e n t e d molasses solutions
o r p u l p m i l l wastes.
O n e of the authors ( A . Y . M . ) reports t h a t d e s i g n
a n d o p e r a t i o n of these c o l u m n s is h a m p e r e d b y l a c k of v a p o r - l i q u i d
e q u i l i b r i u m d a t a , e s p e c i a l l y for m a k i n g p o t a b l e l i q u o r s , w h e r e
small
a m o u n t s of t h e alcohols other t h a n e t h a n o l greatly affect the flavor a n d ,

therefore, the p r o d u c t ' s m a r k e t a b i l i t y .
Prediction of VaporLiquid Equilibrium
Data
A system c o n s i s t i n g of a l i q u i d m i x t u r e a n d v a p o r is i n e q u i l i b r i u m
if, for a n y c o m p o n e n t i, the fugacities i n the v a p o r a n d l i q u i d phases,
fi
a n d /i
are e q u a l .
/i = /,
V
(1)
A s the fugacities are not i n themselves q u a n t i t i e s w h i c h are easily estab

l i s h e d e x p e r i m e n t a l l y , i t is necessary to relate t h e m to easily d e t e r m i n a b l e
quantitiese.g., t e m p e r a t u r e , pressure, a n d c o m p o s i t i o n .
T h i s is d o n e
b y i n t r o d u c i n g the f u g a c i t y a n d a c t i v i t y coefficients * a n d y w h i c h are

defined as f o l l o w s ,
w h e r e y is t h e c o m p o s i t i o n o f c o m p o n e n t f i n t h e v a p o r phase, is the
{
t o t a l pressure of t h e system, x is t h e c o m p o s i t i o n of c o m p o n e n t i i n the

{
l i q u i d phase, a n d
fi
0L
is the f u g a c i t y of c o m p o n e n t i i n the l i q u i d at a
reference state. T h i s reference state is the f u g a c i t y of p u r e l i q u i d i at the

t e m p e r a t u r e a n d pressure of t h e system. E q u a t i o n 1 t h e n becomes
-^
JiXiU
(3)
0lj
A t c o n d i t i o n s w h e n it is safe to assume t h a t t h e gas p h a s e w i l l b e h a v e

i n a n ideal manneri.e.,
at l o w
pressure w i t h a l l c o m p o n e n t s
con
densable
^land/^^P,
Pi
is t h e v a p o r pressure of p u r e l i q u i d i at t h e t e m p e r a t u r e o f t h e system,
a n d e q u i l i b r i u m is d e s c r i b e d b y the e q u a t i o n ,
yP
ytiPi*

(4)
6.
ANDiAPPAN
A N D M C L E A N
Isobaric Vapor-Liquid
Equilibrium
95
A t c o n d i t i o n s w h e r e i t is i n c o r r e c t t o assume i d e a l b e h a v i o r f o r t h e gas
a n d /i
phase,
et al.
are calculated b y procedures described b y Prausnitz
0L
(1).
T h e calculation of y
i9
t h e a c t i v i t y coefficient, establishes * as a f u n c
t i o n of c o m p o s i t i o n , as w e l l as t e m p e r a t u r e a n d pressure. T h i s is d o n e b y
r e l a t i n g * t o t h e excess G i b b s energy G , L e . , b y t h e e q u a t i o n
E
a n d expressing G
o r g , t h e m o l a r excess G i b b s energy, i n terms of

E
composition.
T h e p r o b l e m o f expressing t h e excess G i b b s energy as a f u n c t i o n o f
c o m p o s i t i o n has b e e n researched extensively, a n d m a n y m e t h o d s of v a r y
i n g a c c u r a c y a n d usefulness h a v e b e e n p r o p o s e d . A n extensive d i s c u s s i o n
of these m e t h o d s is g i v e n b y H a l a et al. (2),
m o n expressionse.g.,
w h o s h o w that m a n y c o m
those o f v a n L a a r a n d M a r g u l e s a r e
f r o m t h e g e n e r a l expression of W o h l
C u k o r a n d P r a u s n i t z (4),
deduced
(3).
h o w e v e r , p o i n t o u t that W o h l ' s
expression p r e c l u d e s other expressions f o r t h e c o m p o s i t i o n
general
dependence
of t h e excess free energy, i n c l u d i n g that o f W i l s o n ( 5 ) , w h i c h has b e e n

u s e d b y several authors t o p r e d i c t a n d correlate v a p o r - l i q u i d e q u i l i b r i u m
W i l s o n s equation and the modification proposed b y Renon and
(1,6,7).
P r a u s n i t z (8)
u s e t h e l o c a l m o l e f r a c t i o n concept, p r o d u c e d
because
molecules i n s o l u t i o n aggregate as a result o f t h e v a r i a t i o n i n i n t e r m o l e c u l a r forces.
T h e l o c a l m o l e f r a c t i o n c o n c e p t results i n a m o r e u s e f u l
d e s c r i p t i o n o f t h e b e h a v i o r of m o l e c u l e s i n a n o n - i d e a l m i x t u r e .
The Wilson Equation and the
Two-Liquid
(NRTL)
Non-Random
Equation
T h e W i l s o n e q u a t i o n , u s e d b y P r a u s n i t z et al. (1)
(6,7),
a n d other w o r k e r s
equals or surpasses earlier t w o - p a r a m e t e r equations i n c o r r e l a t i n g
v a p o r - l i q u i d e q u i l i b r i u m d a t a f o r a large n u m b e r of n o n - i d e a l systems.
T h e e q u a t i o n w h i c h is sufficiently d i s c u s s e d elsewhere
( J ) contains t w o
adjustable parameters p e r b i n a r y a n d p r e d i c t s m u l t i c o m p o n e n t e q u i l i b
r i u m d a t a u s i n g t h e b i n a r y parameters only. N o m u l t i c o m p o n e n t e x p e r i
m e n t a l d a t a are necessary as f o r t h e v a n L a a r t y p e e q u a t i o n s o f t h i r d
o r d e r a n d above.
O n e l i m i t a t i o n of t h e W i l s o n e q u a t i o n has b e e n that i t c a n n o t b e
a p p l i e d t o systems w h e r e t h e n o n - i d e a l i t y is s u c h that t w o l i q u i d phases
are
formede.g.,
water-2-methyl-l-propanol
and
water-3-methyl-l-
butanol.

96
E X T R A C T I V E
DISTILLATION
R e n o n a n d P r a u s n i t z ( 8 ) p r o p o s e d a n o t h e r e q u a t i o n , b a s e d also o n
the l o c a l m o l e f r a c t i o n c o n c e p t , w h i c h w o u l d a v o i d this l i m i t a t i o n a n d
c o u l d b e a p p l i e d to partially miscible mixtures. T h e relationship between
a c t i v i t y coefficient a n d l i q u i d p h a s e c o m p o s i t i o n is g i v e n b y t h e e q u a t i o n
i n y ^ i f ^
2
+ t ^ ^ K - i ^ M ^
Gx
ki
'
k-\
where =
(a
2 Gx
kj
k=l
k=l
(5
GjcjXk
number of components
~~ u) is t h e adjustable p a r a m e t e r ( t w o p e r b i n a r y ) s i m i l a r t o that
contained i n the W i l s o n equation.
is a n e m p i r i c a l non-randomness
parameter.
R e n o n a n d P r a u s n i t z ( 8 ) r e c o m m e n d values o f
f o r v a r i o u s classes
of m i x t u r e s . I f these v a l u e s a r e v a l i d t h e n E q u a t i o n 5 has o n l y t w o a d justable p a r a m e t e r s p e r b i n a r y .
T h e N R T L e q u a t i o n w a s u s e d i n this
work.
Experimental
T o test t h e N R T L
equation for predicting V L E data for ternary
mixtures, experimental data for the ternary mixtures a n d for the binary
c o m p o n e n t s o f t h e m i x t u r e s a r e necessary.
A literature survey
showed
t h a t d a t a w e r e n o t r e a d i l y a v a i l a b l e f o r a n y o f t h e ternaries o r f o r t h e
two binaries ethanol-3-methyl-l-propanol a n d 3-methyl-l-butanol-water,
a n d i t w a s therefore necessary to o b t a i n these d a t a e x p e r i m e n t a l l y .
T h e direct measurement of v a p o r - l i q u i d e q u i l i b r i u m data for part i a l l y m i s c i b l e m i x t u r e s s u c h as 3 - m e t h y l - l - b u t a n o l - w a t e r is difficult, a n d
a l t h o u g h stills h a v e b e e n d e s i g n e d f o r this p u r p o s e (9, 10), t h e d a t a w a s
i n d i r e c t l y o b t a i n e d f r o m measurements
o f pressure, P , t e m p e r a t u r e , t,
a n d l i q u i d c o m p o s i t i o n , x. I t w a s also felt that a test o f t h e v a l i d i t y o f

the N R T L
equation i n predicting the V L E data for the ternary mix-
tures w o u l d b e t h e successful p r e d i c t i o n o f t h e b o i l i n g p o i n t . T h i s e l i m inates
the complicated
analytical procedures
necessary
i n the direct
measurement of ternary V L E data.

A modified version of the M-100 b o i l i n g point apparatus, made b y
the James F . S c a n l o n C o . , W h i t t i e r , C a l i f , w a s u s e d ; t e m p e r a t u r e w a s
measured b y a H e w l e t t - P a c k a r d m o d e l 2801A quartz thermometer. A l l
measurements w e r e m a d e at a t m o s p h e r i c pressure w i t h t h e t e m p e r a t u r e
c o r r e c t e d t h e n t o 760 m m H g .

6.
ANDiAPPAN
A N D
M C L E A N
T a b l e I.
Equilibrium
97
F u g a c i t y Coefficients
Component
Temperature,
Water
80
90
130
100
0.9925
0.9960
1.0150
1.0000
Ethanol
80
90
100
1.0015
1.0119
1.0240
1-Propanol
80
90
100
0.9898
0.9954
1.0018
2-Methyl-l-propanol
80
90
100
0.9726
0.9809
0.9904
3-Methyl-l-butanol
80
90
100
130
0.9535
0.9608
0.9686
C.9991
T o extract y f r o m P, t, x, d a t a o b t a i n e d for the b i n a r y system, a

c o m p u t e r p r o g r a m u s i n g the N R T L e q u a t i o n w a s p r e p a r e d . U p o n re
c e i v i n g the i n p u t datai.e., P, x 1 a n d a v a l u e of a, u s u a l l y a r o u n d 0.475
v a l u e s of the adjustable parameters (gi2-g22) a n d ( g 2 i - g n ) w e r e as
s u m e d . T h e a c t i v i t y coefficients w e r e c a l c u l a t e d u s i n g E q u a t i o n 5 a n d
values of y w e r e c a l c u l a t e d u s i n g E q u a t i o n 4. T o justify u s i n g E q u a t i o n
4, values of the f u g a c i t y coefficients w e r e c a l c u l a t e d . T h e s e values
( T a b l e I ) are b e l i e v e d sufficiently near u n i t y to p e r m i t that the effects of
gas p h a s e n o n i d e a l i t y c a n b e i g n o r e d . T h e s u m of t/i a n d y w a s c o m
p a r e d w i t h u n i t y , a n d the p r o c e d u r e w a s r e p e a t e d u n t i l s u m y w a s w i t h i n
a g r e e d l i m i t s of u n i t y . T h i s p r o g r a m also a l l o w e d the c a l c u l a t i n g of
b i n a r y energy parameters u s e d i n p r e d i c t i n g properties of the t e r n a r y
systems.
9
A n a d d i t i o n a l p r o g r a m took the energy parameters of the b i n a r y

systems m a k i n g u p ternary m i x t u r e s a n d c a l c u l a t e d t h e b o i l i n g p o i n t of
the t e r n a r y a n d the e q u i l i b r i u m c o m p o s i t i o n of the v a p o r phase. C o m
p a r i s o n of the m e a s u r e d b o i l i n g p o i n t w i t h the p r e d i c t e d b o i l i n g p o i n t
for the same c o m p o s i t i o n a n d pressure was u s e d as a c r i t e r i o n of successful
p e r f o r m a n c e of the N R T L e q u a t i o n .
T o illustrate the consistency b e t w e e n the t w o programs, d a t a for the
e t h a n o l - w a t e r system r e p o r t e d b y R i e d e r a n d T h o m p s o n ( 11 ) w e r e u s e d .
T h e first p r o g r a m estimated the values of the energy parameters a n d
c a l c u l a t e d the vapor-phase c o m p o s i t i o n , y, w i t h a root m e a n square d e v i a
t i o n ( R M S D ) of 0.00847. T h e m e a n a r i t h m e t i c d e v i a t i o n b e t w e e n the

98
E X T R A C T I V E
A N D
A Z E O T R O P I C
DISTILLATION
s u m y a n d u n i t y w a s 0.0064. T h e e s t i m a t e d parameters w e r e u s e d i n the

s e c o n d p r o g r a m w h i c h p r e d i c t e d t h e same values of y a n d also p r e d i c t e d
the t e m p e r a t u r e of the b o i l i n g m i x t u r e . T h e p r e d i c t e d a n d e x p e r i m e n t a l
t e m p e r a t u r e a g r e e d w i t h a R M S D v a l u e of 0.22C.
T h e p r o c e d u r e e s t a b l i s h i n g the v a p o r - l i q u i d e q u i l i b r i u m d a t a for t h e
b i n a r y system was tested u s i n g the homogeneous
water, a n d the heterogeneous
system,
1-propanol-
system, 2 - m e t h y l - l - p r o p a n o l - w a t e r , u s i n g
the d a t a of M u r t i a n d V a n W i n k l e (12)
and Ellis and Garbett
(9).
T h e R M S D v a l u e b e t w e e n the e x p e r i m e n t a l a n d t h e c a l c u l a t e d values
of y w e r e 0.011 a n d 0.0155, respectively, T h e c o m p a r i s o n b e t w e e n
ex
p e r i m e n t a l a n d c a l c u l a t e d V L E d a t a is s h o w n i n F i g u r e 1 a n d F i g -
Figure
1.
Comparison of calculated
librium data at 760 mm Hg.
Indirectly
Directly
measured, Gadwa
Directly
measured, Murti and Van
and experimental vapor-liquid

1-Propanol (1)-Water
(2).
measured, present work

(15)
Winkle
(12)

equi
6.
ANDiAPPAN
Figure 2.
librium
A N D
M C L E A N
Equilibrium
99
Comparison of calculated and experimental vapor-liquid

equi
data at 760 mm Hg. 2-Methyl-l-Propanol
(1)-Water
(2).
Indirectly measured, present work

Directly measured, Ellis and Garbett
(9)
u r e 2, a n d they agree w e l l e n o u g h to justify u s i n g t h e i n d i r e c t m e t h o d

of e s t a b l i s h i n g t h e V L E d a t a o n t h e system, e t h a n o l - 2 - m e t h y l - l - p r o p a n o l
and 3-methyl-l-butanol-water.
D i r e c t m e a s u r e m e n t of t h e V L E d a t a for t h e e t h a n o l - 2 - m e t h y l - l p r o p a n o l system w e r e also m a d e , u s i n g a M E S 1 0 0 m o d e l e q u i l i b r i u m
s u p p l i e d b y the James F . S c a n l o n C o .
Results and Discussion
Binary System.
T h e e t h a n o l - 2 - m e t h y l - p r o p a n o l system was
to b e h a v e i n a n e x p e c t e d i d e a l w a y .
T h e x-y
found
d a t a , that was d i r e c t l y

100
E X T R A C T I V E AND
Table II.
AZEOTROPIC DISTILLATION
VaporLiquid Equilibrium Data at 760 mm. H g

Ethanol ( l ) - M e t h y l - l - P r o p a n o l
(2)
tc
104.15
101.88
101.55
101.03
98.07
94.67
94.08
90.96
89.34
87.56
86.75
86.11
85.24
84.18
83.67
82.54
81.45
81.11
80.06
Table III.
0.050
0.080
0.085
0.090
0.155
0.220
0.243
0.330
0.382
0.465
0.490
0.510
0.560
0.610
0.635
0.705
0.770
0.800
0.870
0.126
0.200
0.215
0.235
0.332
0.460
0.479
0.595
0.658
0.712
0.742
0.770
0.790
0.817
0.845
0.875
0.915
0.920
0.950
VaporLiquid Equilibrium Data at 760 mm. H g

3-Methyl-1-Butanol ( l ) - W a t e r (2)
t
99.17
97.99
97.82
XJ
Yi
0.0009
0.0024
0.0386
0.0155
0.0031
0.0482
96.60
0.0051
96.27
0.0072
0.0725
0.0932
96.14
0.0073
0.0942
95.90
0.0205
95.26
0.0616
0.1603
0.1694
97.32
0.5766
0.1810
104.03
0.6536
0.2323
109.86
0.7698
0.3495
119.65
0.8873
125.76
126.96
0.9347
0.9427
0.5710
0.7158
128.54
0.9696
0.7449
0.8512
129.84
0.9884
0.9394

6.
ANDiAPPAN
A N D
M C L E A N
Figure
Equilibrium
3.
Vapor-liquid
101
equilibrium
data at 760 mm Hg.
2-Methyl-l-Propanol
(2).
Ethanol
(1)-
Directly measured
y Indirectly measured
Ideal behavior
m e a s u r e d , are p r e s e n t e d i n T a b l e II.
F i g u r e 3 shows t h e c o m p a r i s o n
w i t h the d i r e c t l y m e a s u r e d d a t a , the i n d i r e c t l y m e a s u r e d d a t a , a n d the

data calculated from Raoult's L a w .
T h e v a p o r - l i q u i d e q u i l i b r i u m d a t a for t h e 3 - m e t h y l - l - b u t a n o l - w a t e r
system are s h o w n i n T a b l e I I I a n d F i g u r e 4. T h e b o i l i n g p o i n t measure
ments a g r e e d w i t h those r e p o r t e d i n T i m m e r m a n s (13).
T h e v a l u e of
a =
alcohol-water
0.45 as suggested b y R e n o n a n d P r a u s n i t z ( 8 )
for
systems w a s not suitable. V a r i o u s other values of a w e r e t r i e d , a n d a v a l u e

of
0.3 w a s f o u n d to agree best. T h i s fit c a n b e e s t a b l i s h e d b y u s i n g
the m e t h o d d e s c r i b e d to test t h e consistency of t h e equationsi.e.,

the
102
E X T R A C T I V E
Figure
A N D AZEOTROPIC
DISTILLATION
4.
Vapor-liquid
Table IV.
equilibrium
data at 760 mm Hg.
Butanol (1)-Water ( 2 ) .
3-Methyl-l-
N R T L Parameters for the Binary Systems

Isobaric Systems at 1 A t m .
Reference
E t h a n o l U ) - W a t e r (2)
1 - P r o p a n o l ( i ) - W a t e r (2)
2 - M e t h y l - l - P r o p a n o l (1)-Water
(2)
3 - M e t h y l - l - B u t a n o l U ) - W a t e r (2)
E t h a n o l (1 ) - l - P r o p a n o l (2)
Ethanol (i)-3-Methyl-lB u t a n o l (2)
Ethanol (J)-2-Methyl-lP r o p a n o l [2)
( gia-fW
cal./gram
mole
gai-gu)
cal./gram
mole
16
0.475
0.500
0.475
0.300
0.500
121.0
438.4
611.5
-386.9
465.5
1161.5
1762.9
2475.7
3483.8
-324.5
16
0.475
20.8
7.4
11
15,12
9

6.
ANDiAPPAN
A N D
Table V .
Xj
103
Equilibrium
VaporLiquid Equilibrium Data at 760 mm H g

Water ( l ) - E t h a n o l (2)-l-Propanol (3)
, *
0.1763
0.3742
0.5397
0.7271
0.1642
0.3216
0.4759
0.6350
0.1293
0.2707
0.4214
0.5519
0.1201
0.2421
0 3764
0.4812
0.1246
0.2046
0.3030
0.4071
0.0962
0.1896
0.3096
0.0853
0.1911
0.1125
0.1524
0.0851
M C L E A N
0.0905
0.0992
0.0944
0.0987
0.1920
0.1949
0.1966
0.1984
0.2698
0.2956
0.3123
0.3076
0.4024
0.3935
0.3777
0.3934
0.4861
0.4837
0.4944
0.4939
0.6059
0.6054
0.5907
0.7030
0.7026
0.7007
0.7319
0.8319
y/
0.3133
0.4527
0.5143
0.5345
0.2720
0.3909
0.4526
0.4768
0.2152
0.3297
0.3932
0.4217
0.1793
0.2852
0.3566
0.3797
0.1702
0.2388
0.2936
0.3312
0.1248
0.2045
0.2731
0.1036
0.1889
0.1264
0.1579
0.0920
0.1353
0.1426
0.1503
0.2100
0.2730
0.2649
0.2828
0.3395
0.3752
0.3822
0.4123
0.4510
0.5203
0.4857
0.4750
0.5214
0.5966
0.5744
0.5797
0.5994
0.7064
0.6785
0.6652
0.7814
0.7518
0.7691
0.7792
0.8648
tC
89.13
86.70
86.14
85.75
87.57
85.55
84.63
84.04
86.89
84.47
83.12
82.54
84.85
83.30
82.43
81.60
83.47
82.42
81.35
80.63
82.14
80.92
80.03
80.94
79.65
80.59
79.69
79.24
89.07
86.40
85.60
85.46
87.65
85.47
84.57
83.94
87.19
84.59
83.12
82.51
85.12
83.45
82.47
81.52
83.79
82.65
81.47
80.67
82.39
81.03
80.01
81.11
79.68
80.01
79.30
79.07
"Predicted using N R T L equation.

Measured.
5
c a l c u l a t i o n of the parameters w i t h the first p r o g r a m a n d the use of the

p a r a m e t e r s to c a l c u l a t e t h e i n i t i a l t e m p e r a t u r e .
Ternary System. T h e values of a l l b i n a r y parameters u s e d i n p r e
d i c t i n g t h e t e r n a r y d a t a are s h o w n i n T a b l e I V . T h e p r e d i c t e d values of
the v a p o r - l i q u i d e q u i l i b r i u m datai.e., the b o i l i n g p o i n t , a n d t h e c o m
p o s i t i o n of the v a p o r phase, y, f o r g i v e n values of t h e l i q u i d c o m p o s i t i o n ,
x, are p r e s e n t e d i n T a b l e s V , V I , a n d V I I .
A l s o s h o w n are t h e m e a s u r e d
b o i l i n g p o i n t s for the g i v e n values of the l i q u i d c o m p o s i t i o n . T h e R M S D

v a l u e b e t w e e n t h e p r e d i c t e d a n d m e a s u r e d b o i l i n g p o i n t s for the sys
tems w a t e r - e t h a n o l - l - p r o p a n o l , w a t e r - e t h a n o l - 2 - m e t h y l - l - p r o p a n o l , a n d
w a t e r - e t h a n o l - 2 - m e t h y l - l - b u t a n o l are 0.23C, 0.69C, a n d 2.14C.
It
seems therefore that since t h e N R T L e q u a t i o n successfully p r e d i c t s t e m

p e r a t u r e , t h e p r e d i c t e d values of y c a n b e a c c e p t e d confidently.

104
E X T R A C T I V E
A N D
A Z E O T R O P I C
DISTILLATION
T o test the m e t h o d of p r e d i c t i n g some d i r e c t l y m e a s u r e d t e r n a r y

d a t a , t h e p r e d i c t e d results for the system w a t e r - e t h a n o l - l - p r o p a n o l w e r e
u s e d to c a l c u l a t e r e l a t i v e v o l a t i l i t i e s w h i c h w e r e c o m p a r e d w i t h t h e ex
p e r i m e n t a l l y d e t e r m i n e d v a l u e s of C a r l s o n et al. (14).
This comparison
is s h o w n o n F i g u r e 5. T h e c o m p a r i s o n seems to i n d i c a t e that the m e t h o d

of p r e d i c t i n g is satisfactory a n d gives less scatter t h a n t h e e x p e r i m e n t a l l y
d e t e r m i n e d values of r e l a t i v e v o l a t i l i t y .
Table VI.
VaporLiquid Equilibrium Data at 760 mm H g
Water ( l ) - E t h a n o l (2)-2-Methyl-l-Propanol (3)
x
y."
tC
tC
0.1937
0.0999
0.4203
0.1632
93.28
93.0
0.3582
0.1062
0.5294
0.1574
90.13
89.25
0.5377
0.1003
0.5945
0.1548
88.78
87.67
0.7115
0.1014
0.6098
0.1912
88.09
86.93
0.1589
0.2002
0.3300
0.3163
91.78
0.3156
0.1996
0.4521
0.2854
88.68
91.46
87.72
0.5570
0.1820
0.5377
0.2813
86.88
85.92
0.6352
0.2066
0.5208
0.3492
85.71
84.87
0.1264
0.3072
0.2468
0.4635
90.05
89.89
0.3006
0.2943
0.3947
0.4012
86.86
86.09
0.4103
0.3056
0.4323
0.4161
85.33
84.59
85.1
87.76
0.5562
0.2981
0.4572
0.4474
84.09
0.1255
0.3990
0.2158
0.5602
0.2611
0.3974
0.3274
87.85
85.24
0.3722
0.3897
0.3791
0.5145
0.5041
0.4789
0.3993
0.3930
0.5414
82.53
82.23
0.0959
0.4984
0.1556
0.6666
86.29
86.38
0.1934
0.5010
0.2470
0.6228
84.18
83.96
0.3099
0.4949
0.3135
0.4991
0.3385
82.55
81.32
82.28
0.4006
0.6009
0.6149
0.0954
0.6042
0.7448
83.97
84.08
0.1347
83.95
85.09
83.46
81.10
0.2124
0.5908
0.2339
0.6877
82.05
81.93
0.4614
0.4118
0.3870
0.5465
80.23
0.1021
0.6959
0.1266
0.7982
82.46
81.94
0.1952
0.1955
0.0865
0.7680
0.8764
80.14
0.0757
0.7051
0.8162
80.15
80.11
80.25
0.1805
0.7530
0.1768
0.7997
79.49
79.49
0.0526
0.8987
0.0577
0.9264
79.09
79.19
Predicted using N R T L equation.

* Measured.

81.99
6.
ANDiAPPAN
A N D M C L E A N
105
Equilibrium
Table VII.
V a p o r - L i q u i d Equilibrium Data at 760 mm H g
Water ( l ) - E t h a n o l ( 2 ) - 3 - M e t h y l - l - B u t a n o l (3)
Xi
XJ
y/
y/
tC
t C
0.7422
0.0101
0.8790
0.0198
95.08
94.37
0.4982
0.0127
0.8318
0.0266
97.93
94.67
0.3477
0.0120
0.7503
0.0311
103.20
99.58
0.8455
0.0589
94.46
93.57
100.44
0.7248
0.0303
0.6809
0.8464
0.0729
104.88
0.0565
93.78
0.8412
0.0277
94.56
95.22
0.0241
0.8492
0.0456
95.14
94.13
0.0384
0.7685
0.0826
98.26
95.68
0.6338
0.1773
0.6234
0.3225
89.45
89.41
0.5055
0.2112
05744
0.3604
89.97
89.71
96.20
92.15
0.2944
0.0263
0.7784
0.8878
0.0269
0.0094
0.0344
0.4465
95.40
0.2774
0.1984
0.4574
0.4082
0.2087
0.1867
0.3944
0.4306
99.46
93.92
0.3781
0.3232
0.4331
0.5084
88.31
88.31
86.25
0.6071
0.2999
0.4801
0.4971
84.75
0.1377
0.3002
0.2369
0.6182
96.57
91.73
0.1984
0.3953
0.2684
0.6495
90.32
88.62
0.2802
0.4149
0.3265
0.6180
87.35
87.39
0.4460
0.3727
0.4225
0.5431
85.22
86.62
0.1335
0.4835
0.1774
0.7491
89.05
87.69
0.1857
0.5114
0.2212
0.7262
86.56
86.65
0.3912
0.5172
0.3319
0.6538
81.75
84.07
0.1047
0.6257
0.1248
0.8307
85.20
85.37
0.1939
0.6103
0.2054
0.7648
83.33
84.63
0.2963
0.5946
0.2709
0.7134
81.50
83.62
0.1112
0.6845
0.1247
0.8441
83.31
84.20
0.1353
0.7158
0.1428
0.8359
81.85
83.40
0.2135
0.6820
0.2050
0.7806
83.94
82.97
0.0453
0.8104
0.0511
0.9280
81.67
82.76
0.1022
0.8118
0.1059
0.8824
80.21
82.00
0.1547
0.7925
0.1498
0.8434
79.49
81.51
0.9551
80.02
80.09
0.0312
0.8920
0.0499
0.8998
0.0532
0.9402
79.38
79.45
0.0680
0.8989
0.0706
0.9252
78.96
78.99
0.0343
Predicted using N R T L equation.

Measured.

106
E X T R A C T I V E
A N D
A Z E O T R O P I C
DISTILLATION
>
>
<
LOOfCpCBDO
MOLE
Figure
5.
FRACTION
OF WATER IN
LIQUID
Comparison of calculated and experimental volatilities

panol relative to ethanol in presence of water
of 1-pro-
Indirectly measured, present work

Directly measured, Carbon et al. (14)
Conclusion
T h e n o n - r a n d o m , t w o - l i q u i d (NRTL)
a n d P r a u s n i t z (8)
equation proposed b y Renon
seems to p r e d i c t successfully m u l t i c o m p o n e n t ( t e r n a r y )
m i x t u r e s of a l c o h o l s a n d w a t e r .
T h e alcohols s t u d i e d i n t h i s w o r k etha
n o l , 1 - p r o p a n o l , 2 - m e t h y l - l - p r o p a n o l , a n d 3 - m e t h y l - l - b u t a n o l , w h i c h oc
c u r f r o m the f e r m e n t a t i o n
of
sugar solutions, s h o w h i g h l y n o n - i d e a l
b e h a v i o r i n a q u e o u s solutions a n d present a severe test of t h e effectiveness

of a n y p r e d i c t i o n m e t h o d .
T h e success of the N R T L e q u a t i o n i n u n d e r g o i n g this test w o u l d
suggest that i t w i l l b e a p o w e r f u l t o o l i n t h e d e s i g n of processes i n v o l v i n g
a z e o t r o p i c or extractive d i s t i l l a t i o n . T h e effect of the a d d i t i o n of a t h i r d

6.
ANDiAPPAN
A N D
M C L E A N
Equilibrium
107
c o m p o n e n t t o a difficult to separate b i n a r y m i x t u r e c a n b e p r e d i c t e d w i t h a
d e g r e e of confidence, c e r t a i n l y f o r a l c o h o l - w a t e r mixtures. O n l y e q u i l i b
r i u m d a t a f o r t h e b i n a r y c o m p o n e n t s of t h e system are necessary, a n d this
w o r k shows that e v e n f o r systems of l i m i t e d l i q u i d - p h a s e m i s c i b i l i t y , t h e
N R T L e q u a t i o n c a n b e u s e d to extract t h e necessary i n f o r m a t i o n
from
measurements of b o i l i n g p o i n t , l i q u i d c o m p o s i t i o n , a n d pressure alone.
Literature Cited
1. Prausnitz, J. M., Eckert, C. ., Orye, R. V., O'Connell, J. P., "Computer
Calculations for Multicomponent Vapor-Liquid Equilibria," p. 14,
Prentice Hall, New Jersey, 1967.
2. Hala, E., Pick, J., Fried, V., Vilim, O., "Vapor-Liquid Equilibrium," p. 33,
Pergamon, London, 1967.
3. Wohl, K., Trans. Amer. Inst. Chem. Eng. (1946) 42, 215.
4. Cukor, P. M., Prausnitz, J. M., Int. Symp. "Distillation," p. 73, Inst. Chem.
Eng., London (Sept. 9, 1969).
6. Garrett, G. R., VanWinkle, Matthew,J.Chem. Eng. Data (1969) 14, 302.
7. Gurukul, S. . . ., Raju, . N.,J.Chem. Eng. Data (1966) 11, 501.
8. Renon, H., Prausnitz, J. M., A.I.Ch.E. J. (1968) 14, 135.
9. Ellis, S. R. M., Garbett, R. D., Ind. Eng. Chem. (1960) 52, 385.
10. Othmer, D. F., Gilmont, R., Conti, J. J., Ind. Eng. Chem. (1960) 52, 625.
11. Rieder, R. M., Thompson, A. R., Ind. Eng. Chem. (1949) 41, 2905.
12. Murti, P. S., VanWinkle, Matthew, Ind. Eng. Chem., J. Chem. Eng. Data
(1958) 3, 72.
13. Timmermans, J., "The Physico Chemical Constants of Binary Systems,"
Vol. 4, p. 237, Interscience, New York (1960).
14. Carlson, C. S., Smith, P. V., Jr., Morrell, C. E., Ind. Eng. Chem. (1954)
46, 350.
15. Gadwa, T. W., Chemical Engineering Thesis, M.I.T., 1936.
16. Gay, L., Chim. et Ind. (1927) 18, 187.

7
Demulsification of Crude Oils
Use of Azeotropic
Distillation
LESLIE L. BALASSA and DONALD F. OTHMER

Slate Hill, . Y. 10973 and Polytechnic Institute, Brooklyn, . Y. 11201
Water and often fine sand and silt are held in various crude
oils in permanent emulsions. Particularly crudes obtained by
secondary methods and those from tar sands where water or
steam are used contain water and mineral matter emulsified
therein by the surface forces on small particles and drops.
Azeotropic distillation removes the relatively small amount
of water, using the solvent as an entrainer which dilutes the
crude. This allows: the mineral matter to be separated easily
without using centrifuges with their substantial cost and
wear, free of organic material, so it may be discarded with
out hazards of fire or odors; the bitumen to be recovered
for such use or cracked to give volatile fractions and coked
to an ash-free coke; the water to be obtained as distilled
water for reuse.
" p e t r o l e u m crudes p r o d u c e d b y w a t e r
flooding,
hot water displacement,
pressure steam, or steam i n j e c t i o n u s u a l l y are e m u l s i o n s , either w a t e r i n - o i l o r o i l - i n - w a t e r , a n d are f r e q u e n t l y a c o m b i n a t i o n o f b o t h . E m u l s i o n s

of these h i g h v i s c o s i t y oils often c a n n o t b e b r o k e n a n d d e h y d r a t e d b y
conventional methods.
A n e v e n m o r e difficult p r o c e s s i n g c o n d i t i o n arises w i t h h e a v y b i t u
m i n o u s oils w h i c h a l w a y s c a r r y m u c h sand, c l a y , a n d silt of coarse a n d
s m a l l p a r t i c l e sizes w h i c h s t a b i l i z e the oilwater e m u l s i o n s e v e n m o r e . T h e
b i t u m i n o u s oils h a v e specific gravities of 0.9-1.4 a n d h a v e h i g h viscosi
ties; thus t h e y c a n n o t b e separated f r o m the w a t e r or solids present b y
s e t t l i n g or b y u s i n g the most efficient centrifuges.
D i l u t i n g these e m u l s i o n s o f h e a v y oils w i t h l i g h t
solventse.g.,
kerosene, solvent n a p h t h a , b e n z e n e , etc.reduces the specific g r a v i t y of

the o i l phase of the e m u l s i o n s b e l o w t h a t of w a t e r a n d l o w e r s the v i s 108

7.
B A L A S S A
A N D
O T H M E R
Demulsification
of Crude
109
Oils
cosity so that some of the w a t e r a n d m i n e r a l matters u s u a l l y c a n b e

r e m o v e d b y s e d i m e n t a t i o n , centrifuge, or h y d r o - c y c l o n e .
A d d i t i o n of a l o w viscosity h y d r o c a r b o n solvent often extracts t h e o i l
f r o m the w a t e r ; t h e extract l a y e r of solvent a n d solute separates f r o m the
water. T h e large a m o u n t of solvent n e e d e d to separate e m u l s i o n s of w a t e r
i n a viscous h e a v y o i l is u n e c o n o m i c because of t h e d i l u t e s o l u t i o n n e e d e d
to o b t a i n a c o n t i n u o u s w a t e r phase. A d d i t i o n of solvent, p o s s i b l y u p to a n
e q u a l a m o u n t , is reasonable a n d is d e s i r a b l e to r e d u c e t h e v i s c o s i t y suffic i e n t l y to p u m p a n d transport the h e a v y o i l . A c h e a p a l i p h a t i c s o l v e n t
e.g., k e r o s e n e i s preferable, b u t b i t u m i n o u s o i l fractions are m u c h m o r e
s o l u b l e i n a r o m a t i c solvents, p a r t i c u l a r l y at temperatures near t h e a m bient. H o w e v e r , the w a t e r a n d s o l i d particles are not at a c c e p t a b l e l i m i t s
e v e n after m u c h d i l u t i o n , e s p e c i a l l y i n the presence of fine p a r t i c l e s as
i n some crudes f r o m C a l i f o r n i a a n d V e n e z u e l a a n d p a r t i c u l a r l y f r o m t a r
sands as those i n A t h a b a s c a ( A l b e r t a , C a n a d a ) .
P r o c e s s i n g o i l emulsions f r o m t a r sands is difficult w i t h t h e o i l a n d the
aqueous phase. T h e o i l phase carries m u c h c l a y a n d silt ( s a n d ) of s m a l l
p a r t i c l e size w h i c h are s u s p e n d e d a n d d o not settle o u t e v e n o n p r o l o n g e d
storage.
T h e surface or m o l e c u l a r forces b e t w e e n viscous oils a n d s u c h
fine p a r t i c l e s are m o r e i m p o r t a n t i n d e t e r m i n i n g t h e latter's m o t i o n s , or

l a c k of m o t i o n , t h a n t h e m e c h a n i c a l forces r e s u l t i n g f r o m differences i n
specific gravity.
S o m e particles i n the a q u e o u s phase are w e t b y o i l i n s t e a d of
by
water, a n d these o i l - c o a t e d p a r t i c l e s g i v e a n u n u s u a l l y stable s u s p e n s i o n

for a b o u t the same reason. T h i s o i l i n t h e oil-wet m i n e r a l matter, susp e n d e d i n t h e aqueous phase, makes it u n s u i t a b l e for r e c y c l i n g i n t h e
p r o c e s s i n g o p e r a t i o n or d i s c h a r g i n g b a c k i n t o surface waters.
Also, the
m i n e r a l sludge w h i c h is separated f r o m w a t e r s t i l l contains a s u b s t a n t i a l

percentage of o i l ; it c a n n o t b e d i s p o s e d of e v e n b y r e t u r n i n g i t t o t h e
p l a c e w h e r e it w a s m i n e d or p r o d u c e d . F i r e s h a v e o c c u r r e d f r o m s p o n taneous c o m b u s t i o n r e s u l t i n g f r o m this s l u d g e of fine p a r t i c l e s a n d o i l .
P r i o r processes p r o p o s e d to d e m u l s i f y it are unsatisfactory because
so m u c h o i l is a l w a y s lost i n the aqueous p h a s e o r i n t h e d e w a t e r e d sludge.
A l s o , the content of w a t e r a n d m i n e r a l s i n the o i l separated b y c o n v e n t i o n a l processes is u s u a l l y a b o v e a c c e p t a b l e l i m i t s for p i p e l i n e t r a n s p o r t a t i o n or for r e f i n i n g purposes.
F i n a n c i a l losses are e x p e r i e n c e d i n o i l w a s t e d , i n e q u i p m e n t a n d
c a p i t a l charges of w o r n e q u i p m e n t i n plants, a n d i n l a n d v a l u e of d i s p o s a l
p o n d s . T r e m e n d o u s d i s p o s a l p o n d s of d i s c a r d e d emulsions i n V e n e z u e l a
a n d elsewhere
take u p available land.
I n separating emulsions from
tar sands, the extremely abrasive silt has r u i n e d expensive
centrifuges
a n d makes u s i n g t h e m i m p r a c t i c a l .

110
E X T R A C T I V E
Azeotropic
DISTILLATION
Distillation
T h e w a t e r content of a n e m u l s i o n is r e m o v e d b y d i s t i l l a t i o n , h o w e v e r ,
d i r e c t a n d s i m p l e d i s t i l l a t i o n presents several p r a c t i c a l p r o b l e m s .
I n the
presence of a s o l v e n t - d i l u e n t after p r e l i m i n a r y s e p a r a t i o n of m u c h of the

water
as a c o n t i n u o u s phase, the b a l a n c e is r e m o v e d
by
azeotropic
distillation.
F o r m a n y years w a t e r has b e e n separated f r o m m a n y l i q u i d s b y
a z e o t r o p i c d i s t i l l a t i o n . W a t e r is s u b s t a n t i a l l y i n s o l u b l e n o t o n l y i n the
oils b u t also i n the d i l u e n t s o r solvents. T h u s , the v a p o r pressures of t h e
w a t e r a n d d i l u e n t are a d d i t i v e as i n t h e f a m i l i a r steam d i s t i l l a t i o n s . A
heterogeneous
azeotrope is f o r m e d ; this a l w a y s b o i l s b e l o w t h e b o i l i n g
p o i n t of w a t e r because pressure m u s t b e r e d u c e d f o r w a t e r t o b o i l at t h e
v a p o r pressure of t h e h y d r o c a r b o n .
T h e p r i n c i p l e s of a z e o t r o p i c d i s t i l l a t i o n h a v e often b e e n
(1,2,3,4,5,6,7),
described
a n d a p p l y i n g t h e m gives a s i m p l e m e t h o d of s e p a r a t i n g
w a t e r f r o m its o i l emulsions. T h e l o w - b o i l i n g constituents of a n o i l o r

the d i l u e n t u s e d w o u l d b e t h e entraner ( w i t h d r a w i n g a g e n t ) w h i c h
forms t h e heterogeneous
azeotrope or steam d i s t i l l a t i o n w i t h t h e water.
B e c a u s e of n o n e q u i l i b r i u m b o i l i n g c o n d i t i o n s i n a s i m p l e d i s t i l l a t i o n ,
the vapors m a y n o t c o n t a i n t h e t r u e azeotrope, a n d t h e heat cost m a y b e
too h i g h . T h e r e f o r e a c o l u m n is s t i l l u s e d to r e c t i f y the exact azeotrope
at t h e h e a d of the c o l u m n ; h o w e v e r , o n l y a f e w trays are r e q u i r e d .
T h e azeotrope contains t h e l o w e r h y d r o c a r b o n s of t h e d i l u e n t . I f a
w i d e - c u t f r a c t i o n is u s e d , t h e m o r e v o l a t i l e ones c o m e to t h e t o p of t h e
c o l u m n w i t h the water.
A t a n y t e m p e r a t u r e t h e v a p o r pressure of w a t e r p l u s that o f t h e
entraner, o r t h e effective v a p o r pressure of the m i x t u r e of l i q u i d s o p e r a t i n g as t h e entraner, gives t h e azeotrope's v a p o r pressure. T h e t e m p e r a t u r e w h e r e this s u m m a t i o n c u r v e crosses the a t m o s p h e r i c l i n e , o r
other o p e r a t i n g pressure of t h e d i s t i l l a t i o n , is t h e a z e o t r o p i c
point.
boiling
A close-cut f r a c t i o n o r a single m o r e or less p u r e c o m p o u n d as
a d i l u e n t a n d a z e o t r o p i c w i t h d r a w i n g agent is preferable, a l t h o u g h n o t
necessary.
I f the m i x t u r e loses some o f its m o r e v o l a t i l e
components
at t h e h e a d of the c o l u m n o v e r a p e r i o d of t i m e , t h e a z e o t r o p i c b o i l i n g
p o i n t w i l l g r a d u a l l y rise.
T h e condensate has t w o l i q u i d phases. It r u n s f r o m t h e condenser
to a separator o r decanter w h e r e the w a t e r layer is r e m o v e d f o r d i s c a r d
a n d t h e solvent layer is r e t u r n e d , u s u a l l y as reflux to t h e c o l u m n . T h i s reflux of " a l l o r p a r t " ( t h e solvent l a y e r ) of the condensate after dcantation,
r a t h e r t h a n " p a r t of a l l , " w a s d e v e l o p e d i n 1927 (2)
f o r acetic a c i d d e h y -
d r a t i o n w i t h a n a d d e d solvent as entraner a n d for b u t a n o l d e h y d r a t i o n

u s i n g b u t a n o l itself as t h e entraner.

7.
B A L A S S A
A N D
O T H M E R
Demulsification
of Crude
111
Oils
S e p a r a t i n g w a t e r f r o m a n o i l e m u l s i o n is best d o n e b y a n entraner
a d d e d as a d i l u e n t to the o i l . F o r example, the d i l u e n t a d d e d to t h e o i l
e m u l s i o n is a n a p h t h a f r a c t i o n h a v i n g a n effective v a p o r pressure e q u a l
to that of octane. T h i s n a p h t h a is a d d e d to the o i l , a n d as m u c h w a t e r as
possible is separated; the o i l e m u l s i o n layer w h i c h is n o t b r o k e n contains
the a d d e d n a p h t h a .
OIL, SILT DILUENT

OUT
Figure 1. Flow sheet for removing emulsified water from
crude oil and diluent using azeotropic distilfotion with fixed
amount of entraner
F i g u r e 1 i n d i c a t e s one o p e r a b l e
flow
sheet w h e n this o i l e m u l s i o n
c o n t a i n i n g the n a p h t h a w i l l h a v e a sufficiently l o w v i s c o s i t y to b e p u m p e d
t h r o u g h a t u b u l a r condenser a n d t h e n t h r o u g h a t u b u l a r bottoms
cooler
for heat i n t e r c h a n g i n g a n d r e c o v e r y . It is t h e n p u m p e d to a n u p p e r p l a t e
of a c o l u m n s t i l l . T h i s m i g h t h a v e 1 0 - 1 5 trays d e s i g n e d to a l l o w
ready
passage d o w n w a r d of a n y silt. T h e c o l u m n is thus self-cleaning as m u c h

as possible, b u t p r o v i s i o n s are also m a d e for o p e n i n g to c l e a n m e c h a n i c a l l y ,
i f necessary.
T a b l e I gives several azeotropes o f w a t e r w i t h h y d r o c a r b o n s
and
b u t a n o l , u s e d as entrainers. A s s u m i n g t h e entranerdiluent has the p r o p -

112
e x t r a c t i v e
Table I.
a z e o t r o p i c
d i s t i l l a t i o n
Azeotropes of Water and Entrainers

Composition
by Weight
Temperature,
C (1 atm)
Boiling
Point
Compound
a n d
Azeo.
Temp.
Azeo.
Vapors
Upper
Layers
Lower
Layers
Separated
Layers
Volume,
Toluene
Water
110.6
100
85
79.8
20.2
99.9
0.1
0.1
99.9
82
18
Up
Low
m-Xylene
Water
139.1
100
94.5
60
40
99.95
0.05
0.05
99.95
63.4
36.6
Up
Low
n-Octane
Water
125.7
100
89.6
74.5
25.5
99.98
0.02
0.02
99.98
80
20
Up
Low
Butanol
Water
117.7
100
93
55.5
45.5
77.5
22.5
8.0
92.0
71.5
28.5
Up
Low
erties of o c t a n e , the c o l u m n has a t o p v a p o r t e m p e r a t u r e of 89.6 C .

T h e s e v a p o r s are c o n d e n s e d i n p r e h e a t i n g the f e e d a n d i n another w a t e r c o o l e d condenser i f n e e d e d .
T h e condensate flows to a decanter w h i c h
c o n t i n u o u s l y separates 8 0 %
b y v o l u m e as the d i l u e n t - e n t r a i n e r l a y e r
a n d 2 0 % b y v o l u m e of a w a t e r layer. T h e a m o u n t of e a c h c o m p o n e n t
d i s s o l v e d i n the other layer is so s m a l l that it is d i s r e g a r d e d ; t h u s the
w a t e r l a y e r flows to waste. T h e entraner l a y e r is r e t u r n e d to the t o p of
t h e c o l u m n as reflux to w i t h d r a w m o r e w a t e r , a n d the d r y o i l w i t h sedim e n t passes o u t the b o t t o m a n d t h r o u g h a bottoms exchanger.
T h e silt
n o w settles a n d separates r e l a t i v e l y easily f r o m the o i l w h i c h is d e c a n t e d .

T h e silt is w a s h e d w i t h t h e s o l v e n t - d i l u e n t w h i c h is t h e n r e u s e d w i t h a
f o l l o w i n g o i l e m u l s i o n a n d t h e n s t e a m e d to recover the n a p h t h a .
I n this flow sheet the solvent-diluententraner passes t h r o u g h t h e
system a n d o u t w i t h t h e o i l f o r t r a n s p o r t o r r e f i n i n g a first step w h i c h
m a y r e c o v e r n a p h t h a for reuse. H o w e v e r , i n the c y c l e at the h e a d of the
a z e o t r o p i c c o l u m n w i t h t h e condenser a n d the decanter, f r a c t i o n a t i n g
l i g h t - e n d s f r o m the n a p h t h a p a s s i n g t h r o u g h w i t h the o i l occurs to g i v e the
a z e o t r o p e w i t h w a t e r w h i c h has a c o m p o s i t i o n d e p e n d i n g o n the effective
v a p o r p r e s s u r e of the m i x t u r e of h y d r o c a r b o n s w h i c h stabilizes t h e r e as
t i m e passes. T h i s m a y h a v e a c o n s i d e r a b l y l o w e r b o i l i n g p o i n t t h a n the
n a p h t h a f r a c t i o n , a n d the light-ends congregate a n d b e c o m e the entraner.
S o m e of this m a y b e r e m o v e d f r o m the system b y w i t h d r a w i n g f r o m the
reflux s t r e a m to the c o l u m n . If there are so m a n y l o w ends that the azeot r o p i c b o i l i n g p o i n t goes d o w n , a n a p h t h a f r a c t i o n of s o m e w h a t h i g h e r
b o i l i n g r a n g e is u s e d as the d i l u e n t .
A c t u a l l y this i n d i c a t e s a n o p e r a t i o n c o m p a r a b l e w i t h the d e h y d r a t i o n of m a n y other l i q u i d s w i t h a separate entraner. T h u s , i f no d i l u e n t

A L A S SA
A N D
O T H M E R
Demulsification
of Crude
113
Oils
is necessary to r e d u c e t h e v i s c o s i t y of t h e o i l so that i t m a y b e h a n d l e d
a n d n o d i l u e n t is u s e d to g i v e a p r e v i o u s p a r t i a l d e m u l s i f i c a t i o n , e n o u g h
entraner c o u l d b e selected a n d s u p p l i e d to t h e a z e o t r o p i c system t o
charge the u p p e r p a r t o f the c o l u m n , t h e condenser, decanter, a n d c o n nections. T h e a d d e d entraner w o u l d t h e n w i t h d r a w w a t e r f r o m t h e o i l
e m u l s i o n f e d i n t o a n d o u t of t h e c o l u m n , a n d t h e entraner w o u l d t h e n
act l i k e a m e c h a n i c a l p a r t of t h e system.
T a b l e I shows that, as t h e b o i l i n g p o i n t of the h y d r o c a r b o n u s e d as
t h e entraner increases so does that of t h e azeotrope w i t h w a t e r a n d t h e
p e r c e n t of w a t e r t h e r e i n . A h i g h percentage
of w a t e r i n t h e a z e o t r o p e
is d e s i r e d for the heat r e q u i r e d for t h e d i s t i l l a t i o n , w h i c h is m a i n l y t h a t

of t h e latent heat of t h e w a t e r p l u s that of t h e entraner. Sufficient e n t r a i n e r s h o u l d b e a v a i l a b l e i n the azeotrope f o r reflux to t h e c o l u m n
a l t h o u g h this r e q u i r e m e n t is n o t large.
A l s o , the s o l u b i l i t y o r d i l u t i o n
effect is better w i t h l o w e r - b o i l i n g h y d r o c a r b o n s .
T h u s t h e r e a r e several
factors to be b a l a n c e d i n c h o o s i n g t h e azeotrope.
T h e effect of r e l a t i v e
b o i l i n g points, v a p o r pressures, a n d amounts of different
entrainers i n
t h e i r azeotropes w i t h w a t e r has b e e n d i s c u s s e d as affecting the c h o i c e o f

entrainers for s e p a r a t i n g w a t e r f r o m acetic a c i d ( 5 ) .
However,
that
represents a m u c h m o r e difficult selection because there t h e q u a n t i t y of

reflux is i m p o r t a n t a n d also the solvent characteristics of the entraner
for t h e acetic a c i d also c o n t r o l t h e choice.
However,
t h e o p t i m u m a z e o t r o p i c entraner for w a t e r f r o m a n o i l
e m u l s i o n is p a r t i a l l y selected a c c o r d i n g to those p r i n c i p l e s . T h e highest

b o i l i n g l i q u i d s o b v i o u s l y c a r r y m o r e w a t e r for a g i v e n heat i n p u t .
selected a n d stable t e m p e r a t u r e at t h e t o p of t h e azeo c o l u m n is necessary f o r o p t i m u m o p e r a t i o n , a n d this m i g h t seem to b e s e c u r e d best b y

a pure aromatic.
A l t e r n a t e l y , a p u r e a l i p h a t i c or a close-cut n a p h t h a
f r a c t i o n m i g h t b e o b t a i n e d a n d m a i n t a i n e d i n the a z e o t r o p i c
column.
T h e use of a p u r e c o m p o u n d is n o t advantageous i f a close-cut n a p h t h a

f r a c t i o n is u s e d as a n entraner i n this c o n t i n u o u s o p e r a t i o n because t h e
losses a n d m a k e - u p of s u c h entraner i n a c o l u m n are so s m a l l ; thus, the
effective a z e o t r o p i c b o i l i n g p o i n t r e m a i n s constant.
T h e entraner s h o u l d b e a h y d r o c a r b o n w h i c h has a l o w e r b o i l i n g
p o i n t t h a n t h e light-ends, w h a t e v e r the feedstock of o i l e m u l s i o n ; otherw i s e l i g h t ends c o n t i n u a l l y fractionate i n t o the azeotrope a n d h a v e to b e
removed.
I n other systems i n v o l v i n g a z e o t r o p i c w i t h d r a w i n g agents w i t h
a m i x t u r e of v a r i o u s volatilities, a stable entraner is d e v e l o p e d a n d m a i n t a i n e d at t h e d e s i r e d b o i l i n g p o i n t b y r e m o v i n g p e r i o d i c a l l y some o f t h e

entraner to k e e p its effective b o i l i n g p o i n t sufficiently h i g h .
Sometimes
s m a l l heads c o l u m n s h a v e b e e n i n c o r p o r a t e d to d o this c o n t i n u o u s l y .

114
EXTRACTIVE
Laboratory
AND
AZEOTROPIC
DISTILLATION
Testing
H a v i n g c o n s i d e r e d a b a s i c flow sheet a n d the e l e m e n t a r y p r i n c i p l e s

of a z e o t r o p i c d i s t i l l a t i o n as t h e y m a y b e u s e d , w e c o n s i d e r e d t e s t i n g
emulsions i n the l a b o r a t o r y p r i o r to process design.
T h e first step i n t e s t i n g t h e m a t e r i a l f o r s u i t a b i l i t y o f t h e d e m u l s i f y i n g , d e h y d r a t i n g process is to d i l u t e t h e c r u d e o i l w i t h a solvent w h i c h
is u s e d b y itself or m i x e d w i t h another i n a z e o t r o p i c d e h y d r a t i o n of the
emulsion.
T h e m i n i m u m a m o u n t of solvent w h i c h is sufficient for the
first step is t h a t w h i c h cuts t h e viscosity of the c r u d e e n o u g h to a l l o w

a z e o t r o p i c d i s t i l l a t i o n w i t h o u t excessive f o a m i n g . T h i s m a y r e q u i r e a b o u t
4 0 - 6 0 v o l u m e s solvent p e r 100 v o l u m e s of c r u d e , b u t this r a t i o of solvent,
h o w e v e r , m a y not b e sufficient to r e d u c e the g r a v i t y of the c r u d e b e l o w
that of w a t e r to a l l o w p r e l i m i n a r y dcantation of some of the w a t e r .
T o a c h i e v e this, a v o l u m e of solvent a b o u t e q u a l to t h a t of the c r u d e
m a y h a v e to b e u s e d (sometimes a n e v e n h i g h e r r a t i o of s o l v e n t ) .
By
d i l u t i n g the c r u d e first w i t h t o l u e n e u p to a v o l u m e of 2 0 % of the c r u d e

a n d c o n t i n u i n g the d i l u t i o n w i t h a l i g h t gasoline f r a c t i o n i n the r a n g e
of hexane, octane, or h i g h e r , the g r a v i t y is l o w e r e d w i t h less t o t a l solvent.
A l s o d i l u t i o n w i t h a n a p h t h a f r a c t i o n a l o n e m a y suffice at 80 C .
Each
c r u d e has to b e separately e v a l u a t e d b a s e d o n its properties a n d w a t e r

content. If the w a t e r i n the p e r m a n e n t e m u l s i o n is l o w , it m a y not b e
w o r t h w h i l e to a d d sufficient solvent to separate a w a t e r layer.
T h e w a t e r i n the c r u d e w h i c h is not i n a p e r m a n e n t e m u l s i o n is
d e t e r m i n e d b y d i l u t i n g the c r u d e w i t h a m i x t u r e of toluene a n d a n a p h t h a
f r a c t i o n ; m u c h of the w a t e r together w i t h the water-set i n o r g a n i c m a t t e r
t h e n settles out i n a separatory f u n n e l . If a centrifuge is u s e d , the h i g h
g r a v i t y oil-wet i n o r g a n i c m a t t e r separates w i t h the w a t e r c a r r y i n g w i t h
i t a s u b s t a n t i a l a m o u n t of o i l . T h u s , s i m p l e g r a v i t y s e p a r a t i o n is preferable.
T h e o i l d i l u t e d w i t h the solvent only m a y b e d i s t i l l e d i n a glass flask,
fitted
w i t h a r e l a t i v e l y s i m p l e l a b o r a t o r y c o l u m n . B o i l i n g i n the flask is
a c c o m p l i s h e d w i t h o u t b u m p i n g i f a n i n t e r n a l electric heater w h i c h a l l o w s
l i t t l e superheat is u s e d . T h e a z e o t r o p i c d i s t i l l a t i o n b r i n g s o v e r v a p o r s
w h i c h are c o n d e n s e d . C o n d e n s a t e is separated i n a c o n t i n u o u s glass dec a n t e r w h i c h returns the h y d r o c a r b o n l a y e r to the c o l u m n a n d discharges
the w a t e r layer. W h e n the w a t e r content of the s o l u t i o n is r e d u c e d to
b e l o w 0 . 1 - 0 . 2 % , no w a t e r is v i s i b l e i n the condensate; the t e m p e r a t u r e
at the h e a d of the c o l u m n rises to the b o i l i n g p o i n t of the entraner itself,
a n d the d e h y d r a t i o n is c o m p l e t e . T h e t o t a l w a t e r separated is m e a s u r e d .
T h i s v o l u m e w i t h the w a t e r w h i c h has b e e n separated b y dcantation
after d i l u t i o n a n d before d i s t i l l a t i o n represents the o r i g i n a l a m o u n t of
w a t e r present.

7.
B A L A S S A
A N D
O T H M E R
Demulsification
of Crude
Oils
115
B a t c h a z e o t r o p i c d i s t i l l a t i o n is also a c c o m p l i s h e d i n t h e l a b o r a t o r y
w i t h a s i m p l e flask, condenser, a n d r e c e i v e r w i t h o u t a c o l u m n , c o n t i n u o u s
decanter, a n d c o n t i n u o u s reflux, b u t i t takes m u c h l o n g e r a n d is n o t
c o m p a r a b l e to a p l a n t o p e r a t i o n , w h i c h is d e v e l o p e d f r o m s u c h l a b o r a t o r y
testing.
T h e oil-wet s l u d g e is r e m o v e d f r o m t h e d e h y d r a t e d o i l s o l u t i o n i n
the flask b y s e t t l i n g a n d d e c a n t i n g or c e n t r i f u g i n g .
solvent to free i t of o i l , d r i e d , a n d w e i g h e d .
It is w a s h e d w i t h
T h e w a s h s o l u t i o n is c o m -
b i n e d w i t h the d e h y d r a t e d o i l s o l u t i o n w h i c h contains other solvent a n d

the separate entraner, i f o n e w a s u s e d . S o l v e n t is s t r i p p e d f r o m t h e s o l u t i o n b y d i s t i l l a t i o n to d e t e r m i n e t h e a v a i l a b l e o i l of the c r u d e w h i c h
remains.
A s m a l l a m o u n t of a d d i t i o n a l i n o r g a n i c m a t t e r m a y settle o u t of c r u d e
after a f e w days storage. T h i s is a n extremely s m a l l p a r t i c l e size silt w h i c h
is u s u a l l y less t h a n 0 . 0 5 % of t h e o i l . It m i g h t b e r e m o v e d b y a m o r e
efficient, h i g h e r speed, centrifuge t h a n u s u a l l y a v a i l a b l e . H o w e v e r , s u c h
h i g h s p e e d centrifuges m i g h t b e b a d l y a b r a d e d b y t h e fine silt a n d w o u l d
b e too expensive to u s e i n a c t u a l p r a c t i c e . O n e o r t w o days s e t t l i n g at
120C for example, is a better test m e t h o d a n d is a better p r a c t i c e i n
p r o d u c t i o n i f the necessary storage facilities a r e a v a i l a b l e . A d d i t i v e s t o
flocculate
the fine silt m i g h t also b e u s e d .
Modified Azeotropic
Distillation
C o n t i n u o u s d i s t i l l a t i o n a l w a y s gives a better, m o r e u n i f o r m p r o d u c t
at a l o w e r heat cost a n d u s u a l l y a l o w e r p l a n t cost. A c o n t i n u o u s o p e r a t i o n is essential i n a z e o t r o p i c d i s t i l l a t i o n w h e n a n entraner is a d d e d , o r
it w o u l d necessarily h a v e to b e f r a c t i o n a t e d off to reuse i t after e a c h b a t c h .
S e v e r a l v a r i a t i o n s of t h e flow sheet for a z e o t r o p i c d i s t i l l a t i o n are
possible, e a c h h a v i n g a c o n t i n u o u s d e c a n t e r w h i c h discharges p u r e w a t e r
(less t h a n 0 . 1 % d i s s o l v e d h y d r o c a r b o n o r a r o m a t i c s a n d less t h a n 0 . 0 1 %
for a l i p h a t i c s ). F i g u r e 1 is the s i m p l e s t flow sheet. T h e entraner selected
is c h a r g e d to t h e a z e o t r o p i c c o l u m n a n d r e m a i n s s u b s t a n t i a l l y there, rem o v i n g w a t e r c o n t i n u o u s l y b u t b e i n g a l m o s t u n c h a n g e d i f i t has a l o w e r
b o i l i n g p o i n t t h a n t h e l i g h t ends of t h e feedstock.
T h e reboiler m a y be
h e a t e d b y other w a y s t h a n b y t h e steam s h o w n i n F i g u r e 1.
F i g u r e 2 shows a c o n t i n u o u s a z e o t r o p i c c o l u m n u s i n g a fixed a m o u n t
of entraner w h i c h r e m a i n s i n t h e u n i t . S i n c e reflux is l a r g e l y s u p p l i e d
b y f e e d of the e m u l s i o n near the t o p of t h e c o l u m n , t h e entraner f r o m
the d e c a n t e r passes to a r e b o i l e r a n d is f e d b a c k to t h e t o w e r as vapors.
T h i s gives a m o r e n e a r l y c o u n t e r - c u r r e n t a c t i o n of the a z e o t r o p i c d i s t i l l i n g o p e r a t i o n , a n d a lesser heat i n p u t r e q u i r e d i n t o t h e viscous o i l at
the base of the c o l u m n , u s u a l l y w i t h m o r e or less silt i n suspension w h i l e

116
EXTRACTIVE
AND
AZEOTROPIC
DISTILLATION
CONDENSER >
Figure 2. Flow sheet for removing emulsified water by azeotropic distillation using a vapor feed of the reflux of a fixed
amount of entraner
the b a l a n c e of the heat r e q u i r e m e n t s for the a z e o t r o p i c d i s t i l l a t i o n w o u l d
b e s u p p l i e d to the t h i n , p u r e , entraner i n a separate reboiler.
F i g u r e 3 u t i l i z e s the d i l u t i n g of the o i l e m u l s i o n w i t h the entraner
c o m i n g f r o m the decanter.
T h i s occurs at or near t h e a z e o t r o p i c b o i l i n g
p o i n t . T h i s m i x e r dissolves t h e o i l i n the e m u l s i o n a n d p a r t i a l l y breaks

i t w i t h some of the w a t e r a n d silt b e i n g d e c a n t e d off of the f e e d stream
of p e r m a n e n t
column.
e m u l s i o n a n d entrainer-solvent
g o i n g to the t o p of
the
M o r e entraner m u s t b e u s e d i n this system to s u p p l y t h a t i n
the m i x e r a n d the decanter; h o w e v e r , it is m i x e d w i t h the o i l p a s s i n g

through continuously.
F i g u r e 4 is a m o d i f i c a t i o n o f F i g u r e 3 w h e r e the f u n c t i o n of the m i x e r
i n d i s s o l v i n g the entraner a n d the f e e d of o i l e m u l s i o n a n d t h e f u n c t i o n of
t h e decanter i n s e p a r a t i n g t h e w a t e r layer f o r m e d is t a k e n o v e r b y a n extractor. I t is one o f the several m e c h a n i c a l l y a g i t a t e d types w h i c h washes
o r extracts the o i l out of t h e e m u l s i o n a n d precipitates or discharges as a
raffinate l a y e r the w a t e r a l o n g w i t h most of the silt. T h e r e m a i n i n g perm a n e n t e m u l s i o n o i l l a y e r c a r r i e d b y the d i s s o l v i n g entraner solvent goes
to t h e top of the c o l u m n .

7.
B A L A S S A
A N D
O T H M E R
Demulsification
of Crude
Oils
117
T h e b o t t o m of F i g u r e 4 i n d i c a t e s one system for the h a n d l i n g of t h e

c r u d e w i t h silt f r o m the b o t t o m of t h e c o l u m n before, after, or w i t h o u t
a heat exchanger to r e c o v e r the sensible heat of the bottoms f r o m this
still. A c o n t i n u o u s t h i c k e n e r , of t h e u s u a l r o t a t i n g t y p e w i t h hoes, t h i c k e n s
the s u s p e n d e d silt i n t o a n o i l - m u d w h i c h is r e m o v e d , w a s h e d , a n d steamed
b e f o r e d i s c a r d . T h e solvent r e c o v e r e d f r o m this w a s h i n g of m u d goes
b a c k to t h e f e e d d i s s o l u t i o n . T h e c l e a r c r u d e kerosene s o l u t i o n , n o w free
of w a t e r a n d silt, has kerosene r e m o v e d b y d i s t i l l a t i o n , o r i t is p u m p e d t o
the refinery. O f t e n w h e r e the c r u d e does not c o n t a i n too m u c h w a t e r i n a
p e r m a n e n t e m u l s i o n o r is not too difficult to p u m p , i t w o u l d n o t r e q u i r e
the i n i t i a l d i l u t i o n .
O t h e r v a r i a t i o n s of flows are p o s s i b l e ; i n e a c h case i f m o r e solvente n t r a i n e r is a d d e d to the e m u l s i o n i n a d v a n c e , it is r e c o v e r e d b y d r a w i n g
off a c o r r e s p o n d i n g percentage
of the entraner layer w h i c h discharges
f r o m the decanter a n d r e c y c l i n g i t b a c k to s o l u t i o n t a n k w h e r e i t is a d d e d
to the o p t i m u m p r o p o r t i o n a l a m o u n t of f e e d e m u l s i o n . T h u s , i f kerosene
a n d a n a r o m a t i c solvente.g., t o l u e n e or x y l e n e a r e u s e d i n d i s s o l u t i o n
of t h e e m u l s i o n , t h e a r o m a t i c c h o s e n as the entraner is c o n t i n u o u s l y
Figure 3. Flow sheet using entraner as diluent with premixer

and predecanter for separating some of the silt and water

118
E X T R A C T I V E
A N D
A Z E O T R O P I C
DISTILLATION
Figure 4. Flow sheet using entraner as diluent solvent in an

extractor used to extract oil from an emulsion with water and to
remove a raffinate layer of silt and water (with removal of final
silt from the bottoms stream by a thickener, either before or after
a heat exchanger)
s e p a r a t e d i n the a m o u n t of its a r r i v a l i n the c o l u m n a n d r e c y c l e d b a c k
for c o n t i n u o u s d i s s o l u t i o n i n t h e m i x e r . T h i s is c o n t r o l l e d b y o b s e r v i n g
the temperatures at several m i d s e c t i o n plates, t h e same as t h e a m o u n t of
b u t y l acetate i n the c o l u m n is c o n t r o l l e d i n acetic a c i d d e h y d r a t i o n
(5).
T h e h i g h e r b o i l i n g kerosene is d i s t i l l e d a w a y f r o m t h e c r u d e i n a separate
c o l u m n , or it m a y r e m a i n to t h i n the c r u d e i n its t r a n s p o r t to the refinery.
Comparison of Azeotropic
Demulsification
with GCOS Process
T o e x e m p l i f y the p r o b l e m s of d e m u l s i f i c a t i o n of o i l , some steps i n

the r e c o v e r y of b i t u m i n o u s o i l f r o m t a r sands are c o n s i d e r e d . T h e G r e a t
C a n a d i a n O i l Sands, L t d . ( G C O S ) Process has b e e n d e s c r i b e d i n v a r i o u s

7.
B A L A S S A
A N D
Demulsification
O T H M E R
p u b l i c a t i o n s (e.g., 8),
of Crude
119
Oils
a n d because of the major p r o b l e m s of s e p a r a t i n g
w a t e r a n d a b r a s i v e m i n e r a l s f r o m the c r u d e , o p e r a t i o n a l losses of m a n y
m i l l i o n s of dollars h a v e r e s u l t e d .
Miningoverburden,
r e m o v a l , a n d m i n i n g of tar sands
T r a n s p o r t t a r sands c o n v e y e d , stored, a n d l o a d e d i n extractors

Primary Extraction. T h i s is a c c o m p l i s h e d w i t h steam a n d hot w a t e r
i n r o t a t i n g c o n d i t i o n i n g d r u m s at a b o u t 190 F.
T h e t o t a l mass is p i p e d
i n t o a v e r t i c a l s e p a r a t i o n c e l l w h e r e ( a ) t h e c r u d e b i t u m e n , as a f r o t h ,
rises to the surface a n d is r e m o v e d ; ( b )
a b o t t o m layer c o n t a i n i n g m a i n l y
sand, c l a y , a n d w a t e r w i t h n o t m o r e t h a n a b o u t 2 % b i t u m e n is p i p e d to
the t a i l i n g p o n d ; ( c )
a " m i d d l i n g s " layer w i t h o u t s h a r p d i v i d i n g lines
b e t w e e n the f r o t h a b o v e or the s a n d a n d w a t e r b e l o w . T h i s is a tenacious

e m u l s i o n of b i t u m e n i n w a t e r , s t a b i l i z e d b y a s u b s t a n t i a l a m o u n t of s a n d
a n d c l a y m o s t l y oil-wet.
M o s t of the b i t u m e n is r e m o v e d i n
cells b y a i r - f r o t h i n g . T h e s a n d , clay, a n d w a t e r a n d some

b i t u m e n is p u m p e d to t h e t a i l i n g s p o n d .
scavenger
unrecoverable
B i t u m e n r e c o v e r y is n o t m o r e
t h a n 9 0 % , thus the tailings c a r r y off at least 1 0 % of that o r i g i n a l l y present.

Final Extraction. T h e b i t u m e n f r o m the f r o t h , c o n t a i n i n g s u b s t a n t i a l q u a n t i t i e s of s a n d , clay, a n d w a t e r , is d i l u t e d w i t h n a p h t h a to r e d u c e
its v i s c o s i t y so i t c a n b e p u m p e d r e a d i l y .
It is first p u m p e d to 14 s c r o l l -
t y p e centrifuges to r e m o v e l a r g e m i n e r a l particles a n d t h e n to 26 n o z z l e t y p e centrifuges

A b r a s i o n i n the
charge.
to r e m o v e m o s t of t h e r e m a i n i n g m i n e r a l s a n d
expensive
centrifuges
has b e e n
a major
water.
operational
T h e d i l u t e d b i t u m e n s t i l l contains significant q u a n t i t i e s of w a t e r
a n d h y d r o p h i l i c s a n d a n d clay.
Cracking and Coking.
T h e d i l u t e b i t u m e n is p u m p e d i n t o
d r u m s , w h e r e i t is c r a c k e d to y i e l d gas a n d c r u d e o i l o v e r h e a d ,
goes to the refinery.
coker
which
R e s i d u a l c o k e contains a l l of the r e s i d u a l s a n d a n d
c l a y w h i c h c o u l d not b e r e m o v e d i n the final extraction, a n d therefore

i t is u s e d o n l y as a f u e l for t h e boilers.
I n the a z e o t r o p i c system ( J ) , the m i n i n g a n d transport steps are the
same, also the c r a c k i n g a n d c o k i n g step, except t h a t i t gives a m u c h
i m p r o v e d coke w h i c h is u s e d for m o r e v a l u a b l e p r o d u c t s t h a n as a h i g h
ash f u e l .
I n the p r i m a r y extraction, h o w e v e r , a h y d r o c a r b o n solvent is a d d e d .
This allows a relatively sharp separation between the " m i d d l i n g s " a n d
the aqueous b o t t o m layer.
A f r a c t i o n w i t h b o i l i n g r a n g e of octane
suitable, since i t t h e n becomes the a z e o t r o p i c
entraner for the
A n a r o m a t i c solvente.g., t o l u e n e m i g h t b e better, b u t i t m a y
is
water.
require
another s e p a r a t i o n later.
I n the final e x t r a c t i o n because of solvent a d d i t i o n i n t h e p r i m a r y
extraction, the m i n e r a l matter r e a d i l y separates f r o m the b o t t o m

aqueous
120
EXTRACTIVE
AND
AZEOTROPIC
DISTILLATION
l a y e r i n s t e a d of r e q u i r i n g batteries of expensive centrifuges w i t h c o n s i d e r a b l e d a m a g e r e s u l t i n g f r o m a b r a s i o n of the fine s a n d . A
suitable
s e t t l i n g a i d assists this, a n d the w e t sediment, a l m o s t free of b i t u m e n , is

u s e d as fill. T h e w a t e r contains o n l y a s m a l l a m o u n t of d i s s o l v e d solvent
w h i c h is r e c o v e r e d b y s t r i p p i n g , o r w a s t e d , a n d the w a t e r itself is r e u s e d
or d i s c a r d e d to surface waters as it is e n v i r o n m e n t a l l y
acceptable.
T h e t o p b i t u m e n l a y e r a n d t h e " m i d d l i n g s " l a y e r are c o m b i n e d a n d

are p u m p e d to a n a z e o t r o p i c d i s t i l l a t i o n system, as d i a g r a m m e d i n F i g ures 1, 2, 3, a n d 4. T h e c h o i c e of
flow
sheet d e p e n d s o n the
relative
a m o u n t s of w a t e r r e m a i n i n g a n d the a m o u n t s a n d characteristics of the

m i n e r a l matter. T h e systems of F i g u r e s 3 a n d 4 r e m o v e m o r e w a t e r a n d
silt b e f o r e the a z e o t r o p i c d i s t i l l a t i o n , thus s a v i n g heat. U s i n g t h e system
of F i g u r e 4 i n s t e a d of the t h i c k e n e r , a s i m p l e storage t a n k a l l o w i n g t w o
days residence for settling o u t a l l silt, i n c l u d i n g c o l l o i d a l c l a y w h i c h
passes t h r o u g h the c o l u m n , m a y b e u s e d after the heat exchanger.
If a n a p h t h a f r a c t i o n has b e e n u s e d i n the d i l u t i o n a n d as the entrainer, it is left i n as a d i l u e n t for r e d u c i n g the v i s c o s i t y i n p u m p i n g the
o i l to t h e refinery.
A l t e r n a t i v e l y , some o r a l l is r e m o v e d as a s l i p stream
f r o m t h e reflux g o i n g to the t o p of the a z e o t r o p i c c o l u m n . If toluene or

other a r o m a t i c solvent is u s e d , i t w o u l d b e so r e m o v e d or r e m o v e d i n a
separate d i s t i l l a t i o n for recycle.
O i l - w e t materials, s a n d , a n d clay, s e p a r a t e d f r o m either o i l or w a t e r
layers, are w a s h e d w i t h the solvent o r d i l u e n t u n t i l t h e y are free of b i t u m e n a n d the r e s i d u a l solvent is s t r i p p e d f r o m the m i n e r a l m a t t e r w i t h
steam. T h e m i n e r a l m a t t e r is c l e a n a n d is sent to waste or u s e d as
fill
w i t h o u t d a n g e r of spontaneous c o m b u s t i o n , or i t is u s e d i n cement m a n u facture.
T h e aqueous phases c o n d e n s e d f r o m s u c h s t r i p p i n g a n d f r o m
the d e c a n t e r of the a z e o t r o p i c system has so l i t t l e solvent, i n h u n d r e d t h s

of a percent, that i t is neglected.
It evaporates r e a d i l y i n o p e n storage.
T h i s d i s t i l l e d w a t e r is u s e d for a n y s u i t a b l e p u r p o s e .
R e c o v e r y of the b i t u m e n b y this system has b e e n almost 9 8 % c o m p a r e d w i t h the losses i n the G C O S system, a n d the solvent losses are l o w .
T h e major a d v a n t a g e of this system is e l i m i n a t i o n of the 14-scroll t y p e
centrifuges a n d 26-nozzle t y p e m a c h i n e s u s e d i n the G C O S p l a n t w h i c h
h a v e h a d excessive r e p l a c e m e n t , m a i n t e n a n c e , a n d r e p a i r costs because
o f the a b r a s i v e a c t i o n of the fine solids o n these h i g h speed, p r e c i s i o n
machines.
T h e b i t u m e n o b t a i n e d is the u n m o d i f i e d n a t i v e b i t u m e n w i t h a s u b s t a n t i a l percentage of h i g h m e l t i n g , a l i p h a t i c s o l u b l e c o m p o n e n t s .
These
are separated f r o m t h e l o w m e l t i n g c o m p o n e n t s b y solvent e x t r a c t i o n or

solvent p r e c i p i t a t i o n . T h e h i g h m e l t i n g c o m p o n e n t s are u t i l i z e d i n p r o tective coatings for metals o r i n heat resistant r o a d surface compositions.
If coke is o b t a i n e d f r o m this process, it is free of m i n e r a l m a t t e r a n d

7.
BALASSA AND OTHMER
Demulsification of Crude Oils
121
is used for the same uses as other high grade petroleum cokese.g., in
electrodes or activated carbon, as well as in metallurgical uses where the
high ash content resulting from the residual minerals would prevent that
from the GCOS system being used.
Another advantage is that little water is required in the azeotropic
process since most of the water is recycled and that which is not recycled
is immediately passed to surface waters without environmental damage.
Also, removing all organics from the mineral matters means that these
can be used as fill or otherwise without fire hazard, odors, or other
environmental problems caused by microbiological attacks on any residual
bitumen left on the minerals as in the GCOS process.
Literature Cited
1. Balassa, L. L., U.S. Patent 3,468,789 (Sept. 23, 1969).
2. Clarke, H. T., Othmer, D. F., U.S. Patent 1,804,745 (May 12, 1931).
3. Othmer, D. F., "Encyclopedia of Chemical Technology," 2nd ed., Vol. 2,
p. 839, 1963.
4. Othmer, D. F., U.S. Patent 1,917,391 (July 11, 1933).
5. Othmer, D. F., Chem.&Met. Eng. (1941) 48, 91.
6. Othmer, D. F., Chem. Eng. Progr. (1963) 59, 6, 67.
7. Othmer, D. F., TenEyck, . H., Ind. Eng. Chem. (1949) 41, 2897.
8. "Our Sun," Sun Oil Co., House Publication (Autumn, 1967).

8
Distillation Calculations with Nonideal
Mixtures
a
JOSEPH A. BRUNO, JOHN L . YANOSIK, and JOHN W. TIERNEY

Chemical Engineering Department, University of Pittsburgh,
Pittsburgh, Pa. 15213
A new iteration sequence is presented for solving distillation problems with composition dependent equilibrium and
enthalpy relations. For a steady state, non-reacting system
with m components and n stages, the procedure requires
simultaneous iteration of n(m + 1) variables. These are the
vapor flow rates, the stage temperatures, and all but one
of the liquid compositions. The basic equations for an
equilibrium stage system are presented using matrix notation. The calculation sequence is outlined, and a correction
algorithm based on Newton's method is derived. This requires the calculation of the Jacobian matrix of partial derivatives, and an analytical method for obtaining these derivatives by vector differentiation of the system equations is
presented. This method is much simpler than those used
previously. Modification of the iteration process to hold
selected vapor flows constant is described, and a method of
obtaining starting values for the first iteration is presented.
Results obtained from solution of a sample extractive distillation problem are presented. Quadratic convergence is
obtained near the solution, indicating that the equations
derived for the Jacobian matrix are correct.
^ p h e m a t h e m a t i c a l m o d e l for a steady state e q u i l i b r i u m stage s e p a r a t i o n

process consists of a l a r g e set o f s i m u l t a n e o u s n o n l i n e a r e q u a t i o n s
w h i c h m u s t b e s o l v e d to d e t e r m i n e the phase flow rates, the stage t e m peratures, a n d t h e phase c o m p o s i t i o n . A m a t r i x n o t a t i o n w a s p r e v i o u s l y
p r e s e n t e d (1, 2) w h i c h p e r m i t s w r i t i n g t h e e q u a t i o n s i n a concise f o r m
"Present address: A M O C O Production Co., Tulsa, Okla.
122

8.
BRUNO,
YANOsiK,
A N D
Nonideal
TiERNEY
a n d p r o v i d e s for a n y interstage
flow
123
Mixtures
pattern.
It w a s also s h o w n that
these equations c a n b e a n a l y t i c a l l y differentiated t o o b t a i n iterative algo

r i t h m s w i t h q u a d r a t i c convergence rates near the s o l u t i o n . F o r t h e case
w h e r e the e q u i l i b r i u m ratios are functions o n l y of stage
temperatures
a n d not of c o m p o s i t i o n s , it w a s s h o w n t h a t q u a d r a t i c convergence
can
be o b t a i n e d b y s i m u l t a n e o u s i t e r a t i o n of o n l y the stage temperatures a n d

the v a p o r
flow
rates.
A l l other variables can be obtained b y
solving
n o t h i n g m o r e c o m p l i c a t e d t h a n sets of s i m u l t a n e o u s l i n e a r equations.
O n c e a set of temperatures a n d v a p o r flows are a s s u m e d , t h e equations
b e c o m e l i n e a r i n the r e m a i n i n g variables.
T h u s , for a system w i t h
stages a n d m c o m p o n e n t s , i t is o n l y necessary to iterate o n 2 n v a r i a b l e s

rather t h a n the c o m p l e t e set o f n ( 2 m + 3 ) u n k n o w n s .
If the e q u i l i b r i u m ratios are functions of phase c o m p o s i t i o n s as occurs
i n l i q u i d e x t r a c t i o n or extractive d i s t i l l a t i o n , it is necessary to i n c l u d e
m o r e v a r i a b l e s i n the iterative process.
It w a s later s h o w n ( 3 )
t h a t for
l i q u i d e x t r a c t i o n p r o b l e m s w i t h k n o w n stage temperatures, t h e m i n i m u m
n u m b e r of i t e r a t i o n variables for q u a d r a t i c convergence is ran, t h e v a p o r
flow rates, a n d n(m
v a r i a b l e s is (2m
1) of the phase compositions. T h e t o t a l n u m b e r of

+ 2 ) because t h e temperatures are k n o w n . T h e i t e r a
t i o n sequence is c o m p l e t e l y different for this case as c o m p a r e d w i t h the

p r e v i o u s case w i t h c o m p o s i t i o n i n d e p e n d e n t e q u i l i b r i u m ratios.
D e v e l o p e d here is a c o r r e c t i o n process w i t h q u a d r a t i c
convergence
near t h e s o l u t i o n for p r o b l e m s i n w h i c h the e q u i l i b r i u m ratios are c o m p o

s i t i o n d e p e n d e n t a n d i n w h i c h the stage temperatures are n o t fixed b u t
must be determined.
It is necessary to i n t r o d u c e t h e energy
equations to g i v e the a d d i t i o n a l equations n e e d e d .
balance
T h e derivation fol
l o w s t h e g e n e r a l lines o f that for the l i q u i d e x t r a c t i o n p r o b l e m , b u t t h e

extension is not t r i v i a l . T h e m e t h o d r e q u i r e s the s i m u l t a n e o u s c o r r e c t i o n
of n(m
-f- 1) variables. W e w i l l also present a s i m p l i f i e d m e t h o d of a n a
l y t i c a l l y differentiating the m a t r i x equations w h i c h g r e a t l y reduces
the
w o r k necessary to d e r i v e a c o r r e c t i o n a l g o r i t h m .
I n related
convergence
investigations
Roche
(4)
for c o m p o s i t i o n d e p e n d e n t
constant temperature.
has d e m o n s t r a t e d
quadratic
l i q u i d extraction problems
H e essentially iterates o n a l l (2m
at
+ 2) variables.
N e l s o n ( 5 ) has u s e d the m a t r i x n o t a t i o n of References I a n d 2 t o i n v e s t i

gate systems w h e r e c h e m i c a l r e a c t i o n occurs i n the stages.
Equations for an Equilibrium
The
Separation System
equations d e s c r i b i n g a steady-state
e q u i l i b r i u m stage system
w i t h o u t c h e m i c a l r e a c t i o n are s u m m a r i z e d here.
has b e e n p r e v i o u s l y d i s c u s s e d (1,2,3),
T h e matrix notation
a n d a l l s y m b o l s are defined b e l o w .

124
T h e o v e r a l l m a t e r i a l b a l a n c e e q u a t i o n gives a n i m p o r t a n t r e l a t i o n
b e t w e e n t h e l i q u i d a n d v a p o r flow rate vectors, V a n d L .
BL
+ AV
+ (F*)
3
(1)
T h e m a t r i c e s A a n d a r e fixed b y t h e interstage flow p a t t e r n a n d

together w i t h t h e f e e d m a t r i x F are a s s u m e d to b e g i v e n i n t h e p r o b l e m
statement.
T h e fact that t h e l i q u i d c o m p o s i t i o n s m u s t s u m to a constant (1.0
i f m o l e fractions are u s e d ) i n e a c h stage is g i v e n b y :
(ZO = U
(2)
A s i m i l a r e q u a t i o n c a n b e w r i t t e n f o r t h e v a p o r phase, b u t i t is n o t i n d e
pendent a n d can be derived b y combining Equations ( 1 ) , ( 2 ) , a n d (3).
A m a t e r i a l b a l a n c e c a n b e w r i t t e n f o r e a c h c o m p o n e n t i n e a c h stage,
L X> + A V F> +
= 0; 1 < j < m
(3)
X a n d Y are vectors c o n t a i n i n g l i q u i d a n d v a p o r c o m p o s i t i o n s f o r c o m
j
p o n e n t /'. T h e matrices L a n d V are d i a g o n a l a n d h a v e t h e same elements

o n t h e d i a g o n a l as t h e vectors L a n d V.
A n energy b a l a n c e a r o u n d e a c h stage gives
BLH
+ AY
G +
Q +
(4)
H a n d G are vectors c o n t a i n i n g t h e specific enthalpies of l i q u i d a n d v a p o r

phases i n e a c h stage.
Q is t h e vector o f stage heat duties, a n d Q is t h e
f e e d e n t h a l p y vector.
Q a n d Q are a s s u m e d to b e g i v e n i n t h e p r o b l e m
statement.
T h e e q u i l i b r i u m r e l a t i o n b e t w e e n l i q u i d a n d v a p o r c o m p o s i t i o n s is
given by
>
' K>" X> = ; 1 < j < m

?
(5)
/ a n d a r e t h e a c t i v i t y coefficient m a t r i c e s for v a p o r a n d l i q u i d phases

a n d are d i a g o n a l . F o r i d e a l solutions, t h e y b e c o m e t h e i d e n t i t y m a t r i x .
K
is t h e f u g a c i t y ratio m a t r i x a n d is also d i a g o n a l .
T h e enthalpies a n d e q u i l i b r i u m d a t a are p h y s i c a l properties o f t h e
m i x t u r e s b e i n g separated a n d are a s s u m e d to b e k n o w n e x p l i c i t f u n c t i o n s
of c o m p o s i t i o n s a n d temperatures as f o l l o w s :

8.
B R U N O ,
YANOSIK,
A N D
Nonideal
T I E R N E Y
H{X\
G(Y ,
Y,
. . Y,
T)
(7)
( , X,
. . X,
T)
(8)
( F , 7, . . F ,
T)
(9)
. . X",
T)
X\
125
Mixtures
(6)
K(T)
(10)
E a c h of the a b o v e functions is a s s u m e d to b e c o n t i n u o u s a n d to possess

first derivatives w i t h respect to c o m p o s i t i o n a n d t e m p e r a t u r e .
Also, the
c o m p o s i t i o n of c o m p o n e n t 1 is n o t to b e c o n s i d e r e d as a n i n d e p e n d e n t
v a r i a b l e i n the d e v e l o p m e n t
omitting X
The
and Y
Calculation
w h i c h f o l l o w s , a n d this is e m p h a s i z e d
by
as arguments i n E q u a t i o n s 6 - 9 .
Sequence
E q u a t i o n s 1-10 constitute a set of ( 5 m + 5 ) m a t r i x equations w h i c h

are to b e s o l v e d s i m u l t a n e o u s l y to d e t e r m i n e 2 m c o m p o s i t i o n
vectors,
t w o flow vectors, a t e m p e r a t u r e vector, t w o e n t h a l p y vectors, 2 m a c t i v i t y

coefficient vectors, a n d m f u g a c i t y r a t i o vectors.
T h e solution must be
iterative because the equations are n o n l i n e a r . H o w e v e r , there are v a r i o u s

m e t h o d s of o r g a n i z i n g the c a l c u l a t i o n s , a n d one of o u r p r i m a r y objects
here is to d e v e l o p a n efficient c a l c u l a t i o n order. A t one extreme i t w o u l d
b e possible to c o n s i d e r a l l 5 m +
5 vectors as i t e r a t i o n v a r i a b l e s a n d thus
to h a v e a process w i t h ( 5 m + 5 ) v a r i a b l e s of i t e r a t i o n . It seems o b v i o u s
that a m o r e efficient m e t h o d is to r e d u c e the size of t h e iterative process
b y e l i m i n a t i n g as m a n y of t h e v a r i a b l e s as possible.
I n p r a c t i c e , it is
u n d e s i r a b l e a c t u a l l y to e l i m i n a t e t h e v a r i a b l e s ; i n s t e a d the v a r i a b l e s w i l l
b e d i v i d e d i n t o t w o groups.
T h e first g r o u p is the v a r i a b l e s w h i c h w i l l
b e i t e r a t e d a n d w i l l b e c a l l e d t h e i t e r a t e d or i n d e p e n d e n t v a r i a b l e s ; t h e
second group w i l l be called dependent
variables.
One equation must
b e u s e d t o define e a c h d e p e n d e n t v a r i a b l e , a n d these equations w i l l b e

c a l l e d the d e f i n i n g equations. T h e r e m a i n i n g equations, e q u a l i n n u m b e r
to t h e i n d e p e n d e n t variables, w i l l b e c a l l e d the error equations.
The
i t e r a t i o n sequence w i l l t h e n b e to assume first a set of values for the i n d e

p e n d e n t variables a n d t h e n to solve t h e d e f i n i n g equations for the de
p e n d e n t variables.
T h e error equations are t h e n u s e d to correct
the
i n d e p e n d e n t v a r i a b l e s , a n d the process is repeated.

T h e n u m b e r of i n d e p e n d e n t variables s h o u l d g e n e r a l l y b e as s m a l l
as possible. A l s o , the d e f i n i n g equations s h o u l d p e r m i t s i m p l e c a l c u l a
t i o n of the d e p e n d e n t variables, a n d t h e c o r r e c t i o n process itself s h o u l d
b e s i m p l e a n d efficient.
H e r e the set of i n d e p e n d e n t v a r i a b l e s has b e e n
c h o s e n to b e as s m a l l as possible subject t o t h e l i m i t a t i o n t h a t the d e f i n i n g

equations
r e m a i n l i n e a r i n the
dependent
variables.
The
correction

126
EXTRACTIVE
AND AZEOTROPIC
DISTILLATION
a l g o r i t h m is also l i n e a r a n d is t h e m u l t i v a r i a b l e f o r m o f t h e N e w t o n Raphson method.

T h e set o f i n d e p e n d e n t v a r i a b l e s w h i c h satisfies these r e q u i r e m e n t s
is the v a p o r flow v e c t o r V , the l i q u i d p h a s e c o m p o s i t i o n s , X t o X , a n d
2
the t e m p e r a t u r e v e c t o r T . T h e c a l c u l a t i o n sequence is,

a. V a l u e s are a s s u m e d f o r ( V , X , X , . . X , T ) .
2
b. T h e l i q u i d flow vector L is c a l c u l a t e d u s i n g E q u a t i o n 1.
c. E q u a t i o n 2 is u s e d to c a l c u l a t e X .
1
d . E q u a t i o n 3 is u s e d m times t o c a l c u l a t e Y ^ ,.. Y .
e. E q u a t i o n s 6 - 1 0 a r e u s e d t o c a l c u l a t e t h e d e p e n d e n t v a r i a b l e s
H, G, , , a n d K . A l l v a r i a b l e s h a v e n o w b e e n e v a l u a t e d f o r the c u r r e n t
set o f i n d e p e n d e n t v a r i a b l e s .
f. C u r r e n t values f o r a l l v a r i a b l e s are s u b s t i t u t e d i n t o the error e q u a
tions, w h i c h a r e E q u a t i o n s 4 a n d 5. I f t h e equations a r e satisfied, t h e
i t e r a t i v e process is t e r m i n a t e d . O t h e r w i s e , t h e i n d e p e n d e n t v a r i a b l e s
m u s t b e c o r r e c t e d , a n d the c a l c u l a t i o n r e p e a t e d f r o m Step b .
1
The Jacobian
Correction
Matrix
T h e o n l y u n d e f i n e d step i n t h e c a l c u l a t i o n sequence p r o p o s e d a b o v e
is t h e c o r r e c t i o n o f the i n d e p e n d e n t v a r i a b l e s i n step f. A l i n e a r correc
t i o n process is g i v e n b y
( J ) v { ( C )
(C)v}
(11)
(D)v
w h e r e C is t h e d i r e c t s u m o f t h e i n d e p e n d e n t v a r i a b l e s i n t h e o r d e r
( V , X , X , . . X , T ) , a n d D is the d i r e c t s u m o f the error vectors, defined as
2
= AY
k
***; 1 < k < m
= BL H + AVG
T h e most r a p i d convergence
+ Q+ Q
(12)
(13)
o f E q u a t i o n 11 t o t h e s o l u t i o n is o b
t a i n e d w h e n J is t h e J a c o b i a n m a t r i x , defined as t h e m a t r i x i n w h i c h
e a c h element is t h e p a r t i a l d e r i v a t i v e o f o n e of t h e errors w i t h respect
to o n e o f t h e i t e r a t i o n v a r i a b l e s w i t h a l l other i t e r a t i o n v a r i a b l e s h e l d
constant. T h u s , a n estimate o f the effect o f e a c h c h a n g e i n a n i t e r a t i o n
v a r i a b l e o n e a c h o f t h e errors i s i n c l u d e d i n t h e c o r r e c t i o n . T h e d i s a d
v a n t a g e i n u s i n g t h e J a c o b i a n m a t r i x is t h e large n u m b e r o f d e r i v a t i v e s
n e e d e d , (mn + n ) , a n d a s i m p l e means o f o b t a i n i n g these d e r i v a t i v e s is
2
needed.
W e h a v e f o u n d that v e c t o r differentiation o f t h e m a t r i x e q u a
tions g i v e n a b o v e does g r e a t l y s i m p l i f y t h e d e r i v a t i o n of t h e e q u a t i o n s
for c a l c u l a t i o n o f t h e J a c o b i a n .
B y vector differentiation w e m e a n t h e o p e r a t i o n o f differentiating
one v e c t o r w i t h respect to a s e c o n d vector.
T h e result is a m a t r i x i n
w h i c h e a c h c o l u m n is t h e d e r i v a t i v e o f t h e first v e c t o r w i t h respect t o

8.
B R U N O ,
YANOSiK,
Nonideal
A N D T B E R N E Y
127
Mixtures
one o f t h e elements o f t h e s e c o n d vector. F o r e x a m p l e ( dL/dV ) is a n b y

m a t r i x i n w h i c h t h e j t h c o l u m n is (dL/dVj),
a n d t h e ij element is
(dk/dv,).
J c a n n o w b e defined b y v e c t o r derivatives.
p a r t i t i o n e d into (m + l )
F i r s t , h o w e v e r , i t is
s u b m a t r i c e s , e a c h o f size b y n . S u b s c r i p t s
are u s e d t o designate t h e submatrices.
Thus, from the definition of the
Jacobian matrix, w e obtain
w ' ' * J* =
{ ~ ; 2
f^;k
(15)
< k <m
(16)
m+l
B e f o r e p r o c e e d i n g w i t h t h e e v a l u a t i o n o f E q u a t i o n s 1 4 - 1 6 , some use
f u l relations a m o n g t h e v a r i a b l e s w i l l b e d e r i v e d b y differentiating t h e
d e f i n i n g equations ( E q u a t i o n s 1-3 a n d 6 - 1 0 ) w i t h respect t o t h e i t e r a t i o n
variables.
T h e s e results w i l l b e u s e d w h e n
t h e error equations a r e
differentiated i m p l i c i t l y .
F r o m t h e o v e r a l l m a t e r i a l b a l a n c e , E q u a t i o n 1,
%
Because X . . X
= -
_ 1
A = -
(17)
are iteration variables,

I l ; 2 < j, k < m
(18)
jk
where 8
jk
0 if /^
t h e fact that X
k a n d equals 1.0 i f / k. F r o m E q u a t i o n 2 a n d
is n o t a n i t e r a t i o n v a r i a b l e ,
g -
; 2 < j < m
D i f f e r e n t i a t i n g E q u a t i o n 3 w i t h respect to i n d e p e n d e n t
(19)
liquid
compo-
sitions.
AY*
yû= ~ Y-'S
-1
<h k <m
L = v-iR-i L; 2 < k < m

(20)
(21)
128
EXTRACTIVE
AND
AZEOTROPIC
DISTILLATION
F o r Y , a different result is o b t a i n e d because of E q u a t i o n 19.

1
T o d e r i v e E q u a t i o n s 20 a n d 2 1 , i t m u s t b e r e m e m b e r e d
differentiation is w i t h respect to X ,
that the
h o l d i n g V , T , a n d a l l other i n d e
p e n d e n t l i q u i d c o m p o s i t i o n s constant. W i t h V constant, L m u s t also b e

constant because of E q u a t i o n 17.
E q u a t i o n 3 w i l l n o w b e differentiated w i t h respect to V, h o l d i n g
and X . . X
2
constant. I n this case L is not constant, a n d differentiation
of the first t e r m B L X ' causes difficulty because L is a d i a g o n a l m a t r i x

a n d not a vector.
T h i s c a n b e r e s o l v e d b y r e w r i t i n g B L X ' as BXJL,
n o w L is a vector.
and
T h i s s p e c i a l t y p e of c o m m u t a t i v i t y for t h e p r o d u c t
of a d i a g o n a l m a t r i x a n d a vector is u s e d a g a i n i n the p r o d u c t A V Y ' a n d

frequently i n the derivations w h i c h follow.
by V
T h e d e r i v a t i v e of E q u a t i o n 3
gives,
=Y
dV
P a r t i a l derivatives
-1
{R
- 1
S - Y} ;
7
< j <
of the p h y s i c a l properties
(22)
given by
Equations
6 - 1 0 w i l l also b e n e e d e d i n the d e r i v a t i o n s of t h e J a c o b i a n submatrices.

H o w e v e r , the exact f o r m of E q u a t i o n s 6 - 1 0 is not k n o w n a n d w i l l v a r y
f r o m p r o b l e m to p r o b l e m .
T h e c o n v e n t i o n w i l l b e a d o p t e d that a n y
p a r t i a l d e r i v a t i v e i n v o l v i n g a p h y s i c a l p r o p e r t y is to b e i n t e r p r e t e d u s i n g
the v a r i a b l e s
given
as arguments
i n Equations 6-10.
For
( d G / d Y ) means the p a r t i a l d e r i v a t i v e of G w i t h respect to Y

2
Y ... Y
3
and
constant. A l l vector
derivatives
example,
2
holding
of p h y s i c a l p r o p e r t y
vectors w i l l b e d i a g o n a l matrices. T h i s is necessary because t h e p h y s i c a l

properties i n a n y one stage are f u n c t i o n s o n l y of t h e c o m p o s i t i o n s a n d
t e m p e r a t u r e i n that stage.
The Jacobian
Submatrices
S e v e n different e q u a t i o n s are n e e d e d to c a l c u l a t e the v a r i o u s s u b matrices of J :

1. T h e first g r o u p of s u b m a t r i c e s is o b t a i n e d b y differentiating t h e
error vector w i t h respect to i n d e p e n d e n t c o m p o s i t i o n s . T h e g e n e r a l
e q u a t i o n is
dX
" ~
dX
(23)
K'X'
- -
dX"

8.
YANOsiK,
B R U N O ,
Nonideal
A N D TiERNEY
129
Mixtures
F o r 2 ^ j,k ^ m, E q u a t i o n s 18 a n d 2 0 are u s e d t o o b t a i n
2. F o r / =
2<j,k<m
1 i n E q u a t i o n 23, E q u a t i o n s 19 a n d 21 are u s e d
Ju = A ^ R - i L
Y^R-'L
+ P K
(24)
K
^ ) ;
2 < k < m
3. T h e derivatives of t h e m a t e r i a l b a l a n c e errors w i t h respect t o

v a p o r flows are e v a l u a t e d :
dE'
dV
a n d t h e n u s i n g E q u a t i o n 22
Jyi = Y~ (^'R ~ YO + '

1
(|^)
-1
( R X S - Y )
(y" )
1
_ 1
(26)
1 < j < m
4. T h e energy b a l a n c e errors are next differentiated w i t h respect to

v a p o r flows.
dE
dV
|,(|)(f)
<w
U s i n g E q u a t i o n s 17 a n d 22
lm i,i
+
= - B H R + A G + A
(J^j Y"
(E X E
-1
- Y ) (28)
p
5. T h e derivatives of t h e energy balances w i t h respect to c o m p o sitions are,
dE
~dX
m+1

130
EXTRACTIVE
A N DAZEOTROPIC
DISTILLATION
T h e n , u s i n g E q u a t i o n 20, a n d after some rearrangement.
= B L
(J^ - A (Jf^j R - L
2
(30)
< k< m
6. T h e derivatives o f the m a t e r i a l b a l a n c e errors w i t h respect t o

are next c a l c u l a t e d .
-faI'(^)-M'(^)-S*(S.>
1<j < m
(31)
7. F i n a l l y , the d e r i v a t i v e o f the energy b a l a n c e w i t h respect t o

gives,
^ ' - W ,
Change
of Iteration
BL(g) Av(g)
(32)
Variable
T h e J a c o b i a n m a t r i x d e v e l o p e d a b o v e is b a s e d u p o n a specific m o d e l
of a staged system i n w h i c h t h e flow rates, the temperatures, a n d the
phase c o m p o s i t i o n s are a l l u n k n o w n a n d m u s t b e d e t e r m i n e d . A v a r i a
t i o n o f this m o d e l w h i c h often occurs i n p r a c t i c e r e q u i r e s that a s o l u t i o n
b e f o u n d i n w h i c h one or m o r e o f the flows has a fixed v a l u e . I t is r e l a
t i v e l y s i m p l e t o m o d i f y t h e i t e r a t i o n p r o c e d u r e a n d the J a c o b i a n m a t r i x
for the case o f fixed v a p o r flows b y s u b s t i t u t i n g one o f the elements o f Q,
the heat e x c h a n g e vector, for e a c h o f the v a p o r flows w h i c h is to b e
T o i n t e r c h a n g e t h e v a r i a b l e s Vi a n d q
jy
fixed.
the f o l l o w i n g p r o c e d u r e c a n
b e u s e d . T h e J a c o b i a n m a t r i x is first m o d i f i e d b y setting t o z e r o the i t h

column o f e a c h o f the s u b m a t r i c e s J * * for k =
1 t o m. T h e i t h c o l u m n
contains the effect o f c h a n g i n g of Vi o n e a c h element o f E; because q, does

n o t enter i n t o a n y o f t h e m a t e r i a l b a l a n c e e q u a t i o n s , this c o l u m n b e
comes zero. T h e i t h c o l u m n o f Jm+, is set e q u a l to the ; t h c o l u m n o f a n
b y i d e n t i t y m a t r i x because q$ enters o n l y the o n e energy b a l a n c e
e q u a t i o n . U p o n s o l v i n g for the c o r r e c t i o n vector [ ( C ) v + i ( C ) v ] t h e
i t h element is n o w the c o r r e c t i o n for q$. T h e c o r r e c t i o n to is zero.
T h i s p r o c e d u r e c a n o n l y b e u s e d for fixed v a p o r flows. I f l i q u i d
flows
are t o b e fixed, a m o r e c o m p l i c a t e d p r o c e d u r e is n e e d e d a n d w i l l n o t
b e d e v e l o p e d here. F o r s i m p l e c o u n t e r c u r r e n t systems i t is u s u a l l y pos
sible to fix p r o d u c t l i q u i d flows b y fixing c e r t a i n v a p o r flows. A n o b v i o u s
m o d i f i c a t i o n o f the a b o v e p r o c e d u r e c a n b e u s e d t o fix temperatures i f
desired.

8.
B R U N O ,
YANOsiK,
A N D
TiERNEY
Initial Values for Iteration
Nonideal
131
Mixtures
Variables
A n i m p o r t a n t p a r t of the i t e r a t i o n p r o c e d u r e is to select i n i t i a l values

for t h e i t e r a t i o n v a r i a b l e s
( V,X
... X , T ) .
The
correction
sequence
g i v e n b y E q u a t i o n 11 w i l l c o n v e r g e for s t a r t i n g values sufficiently close

to t h e s o l u t i o n . T h e r e is no s i m p l e w a y of k n o w i n g w h e t h e r a g i v e n set
of i n i t i a l values is w i t h i n this convergence
range or not.
Every
effort
s h o u l d b e m a d e to m a k e t h e i n i t i a l values as g o o d as possible.
The
m e t h o d w e h a v e u s e d is d e s c r i b e d here.
T h e temperatures of the r e b o i l e r a n d the condenser are first e s t i m a t e d
u s i n g w h a t e v e r i n f o r m a t i o n is a v a i l a b l e . T h e temperatures of the i n t e r m e d i a t e stages are t h e n o b t a i n e d b y l i n e a r i n t e r p o l a t i o n b e t w e e n
con-
denser t e m p e r a t u r e a n d r e b o i l e r t e m p e r a t u r e .
T h e i n i t i a l v a p o r flows are t h e n c a l c u l a t e d b y e s t i m a t i n g the l i q u i d
a n d v a p o r enthalpies a n d s o l v i n g s i m u l t a n e o u s l y E q u a t i o n 1, t h e o v e r a l l
m a t e r i a l b a l a n c e , a n d E q u a t i o n 4, t h e e n e r g y b a l a n c e . T h e c o m p o s i t i o n s
are u n k n o w n for the e n t h a l p y c a l c u l a t i o n . T h e p r o c e d u r e w e h a v e u s e d
is to set a l l c o m p o s i t i o n s i n a l l stages e q u a l to 1/m; this is a r o u g h
approximation.
A f t e r o b t a i n i n g V a n d L , the a c t i v i t y coefficients a n d f u g a c i t y ratios
are c a l c u l a t e d u s i n g 1/m as t h e average c o m p o s i t i o n i n a l l stages.
Then
E q u a t i o n s 3 a n d 5 are s i m u l t a n e o u s l y s o l v e d to g i v e the l i q u i d phase

c o m p o s i t i o n s . T h e s e c o m p o s i t i o n s for e a c h stage are t h e n s u m m e d a n d
n o r m a l i z e d to one. T h e s e serve as t h e first estimates for X , . . X .
2
Modification
The
of Correction
requirement
Algorithm
that a l l of the v a r i a b l e s l i e w i t h i n
reasonable
p h y s i c a l b o u n d s c a n b e i n c o r p o r a t e d i n t o the c o r r e c t i o n a l g o r i t h m .
h a v e d o n e this b y s p e c i f y i n g t h a t at a l l times the v a p o r a n d l i q u i d
m u s t b e p o s i t i v e or zero; t h e phase c o m p o s i t i o n s m u s t n o t b e
We
flows
negative
or greater t h a n one; a n d the temperatures m u s t l i e w i t h i n p r e d e t e r m i n e d

l i m i t s . I f at a n y t i m e d u r i n g t h e c o r r e c t i o n process these l i m i t s are exc e e d e d , the c u r r e n t i t e r a t i o n is t e r m i n a t e d . I f it is the first i t e r a t i o n , t h e n
a n e w set of i n i t i a l values w i l l b e n e e d e d .
If i t is the s e c o n d or a later
i t e r a t i o n , t h e n i t is a s s u m e d t h a t the corrections m a d e i n t h e p r e v i o u s
i t e r a t i o n w e r e too large, a n d the c u r r e n t i t e r a t i o n is r e p e a t e d u s i n g oneh a l f the corrections p r e d i c t e d i n t h e p r e v i o u s step. It m a y b e necessary
to repeat this process several t i m e s b e f o r e a l l v a r i a b l e s satisfy t h e g i v e n
b o u n d s . If d u r i n g a n y i t e r a t i o n , m o r e t h a n 10 h a l v i n g s of the c o r r e c t i o n
are n e e d e d , w e h a v e t e r m i n a t e d c a l c u l a t i o n s a n d a s s u m e d t h e process
was
diverging.

132
EXTRACTIVE
Application
AND
AZEOTROPIC
DISTILLATION
to a Sample Problem
T h e results o b t a i n e d i n the s o l u t i o n of a sample p r o b l e m are s u m

m a r i z e d here to i l l u s t r a t e the a p p l i c a t i o n of the m e t h o d .
distillation problem from Oliver
(6)
An
extractive
was used i n w h i c h methylcyclo-
hexane is separated f r o m toluene b y a d d i n g p h e n o l . T h e c o l u m n contains

11 stages ( i n c l u d i n g the r e b o i l e r a n d c o n d e n s e r ) a n d has a f e e d of 0.4
m o l e s / u n i t t i m e of m e t h y l c y c l o h e x a n e a n d 0.6 m o l e s / u n i t t i m e of toluene
to the f o u r t h stage f r o m the r e b o i l e r a n d 4.848 m o l e s / u n i t t i m e of p h e n o l
to t h e f o u r t h stage f r o m the condenser. W e u s e d t h e same p h y s i c a l p r o p
e r t y correlations as O l i v e r . T h e a c t i v i t y coefficients w e r e o b t a i n e d f r o m
a m u l t i c o m p o n e n t f o r m of the V a n L a a r E q u a t i o n
Table I.
(7).
Norms for Successive Iterations of Sample Problem
Iteration
Composition,
1
2
3
4
5
6
7
8
9
Energy Balance,
2.9
1.6
1.5
1.4
1.2
5.8E-1
7.8E-2
1.7E-3
5.0E-6
2.8E4
1.6E4
7.2E4
3.2E4
9.8E3
7.5E3
1.5E3
8.1
2.0E-1
Results for successive iterations of a t y p i c a l r u n are s h o w n i n T a b l e I.

T h e c o m p o s i t i o n n o r m is defined as t h e E u c l i d e a n n o r m of the c o m p o s i t i o n
errors
/ n
9 =
(
V = i y=i
2\
(e )
i3
(33)
)
/
a n d t h e energy b a l a n c e n o r m as
(<Wi)
(34)
V a l u e s for these n o r m s are g i v e n i n T a b l e I at e a c h i t e r a t i o n . A t i t e r a t i o n

9 the m a x i m u m error i n a n y e q u i l i b r i u m e q u a t i o n is 2
10" , a n d the
6
m a x i m u m energy b a l a n c e error is 0.09 B t u / u n i t t i m e .

T h e t o t a l t i m e r e q u i r e d for the n i n e iterations i n T a b l e I w a s a b o u t
4 m i n o n a n I B M 360/50 of w h i c h 1.5 m i n w a s e x e c u t i o n time.
The
J a c o b i a n w a s c a l c u l a t e d for e a c h iteration.
T h e results f r o m some other runs are s u m m a r i z e d i n T a b l e II.
e a c h r u n the values of v
and u
For
w e r e h e l d constant b y m a k i n g qx a n d

8.
B R U N O ,
YANOSiK,
A N D
<7u i t e r a t i o n variables.
Nonideal
TiERNEY
133
Mixtures
A U other heat duties,
w e r e set to zero.
F o r e a c h r u n i t is necessary to estimate the r e b o i l e r a n d condenser t e m peratures to i n i t i a t e c a l c u l a t i o n s . T h e s t a r t i n g v a l u e m e t h o d
described
p r e v i o u s l y w a s u s e d to c a l c u l a t e a l l other s t a r t i n g values for the i t e r a t i o n

variables. V a l u e s of u n a r o u n d 0.4 m o l e s / u n i t t i m e are i n t e r e s t i n g because u n is the v a p o r p r o d u c t a n d s h o u l d b e m o s t l y m e t h y l c y c l o h e x a n e .
Discussion
T h e last t w o iterations i n T a b l e I c l e a r l y i n d i c a t e q u a d r a t i c c o n v e r g e n c e rates. T h i s is e s p e c i a l l y e v i d e n t i n the c o m p o s i t i o n n o r m w h e r e
the error is r o u g h l y s q u a r i n g i n e a c h i t e r a t i o n . . T h e e n e r g y b a l a n c e n o r m
for the last i t e r a t i o n does n o t decrease as m u c h as i t s h o u l d , b u t this
u n d o u b t e d l y results f r o m round-off errors i n t h e c o m p u t e r w h e n u s i n g
single
precision arithmetic.
The
m a x i m u m energy
balance
error
in
i t e r a t i o n 9 is 0.09 B t u / u n i t t i m e , a n d the enthalpies w h i c h are b e i n g

s u m m e d i n the energy b a l a n c e e q u a t i o n are of the o r d e r of 50,000 B t u /
unit time.
T h e fact that q u a d r a t i c convergence
is o b t a i n e d is s t r o n g
e v i d e n c e that the J a c o b i a n m a t r i x has b e e n c o r r e c t l y c a l c u l a t e d a n d t h a t

the d e r i v e d equations are correct.
It is u n l i k e l y that the n o r m s c o u l d
decrease as t h e y d o i n the last t w o iterations i f the J a c o b i a n w e r e incorrect.

T h e first seven iterations i n T a b l e I s h o w s l o w l i n e a r
convergence.
T h e c o r r e c t i o n - h a l v i n g p r o c e d u r e o u t l i n e d p r e v i o u s l y w a s u s e d at least
once i n iterations 2 - 6 . T h e other r u n s i n T a b l e II b e h a v e d s i m i l a r l y . A l l
took m o r e t h a n n i n e iterations, a n d for e a c h case the n o r m s w o u l d decrease s l o w l y ( e v e n o c c a s i o n a l l y r i s i n g for one i t e r a t i o n )
u n t i l the last
t w o or three iterations w h e n t h e y w o u l d d r a m a t i c a l l y decrease.

the r u n s d i d not
Two
T h e results i n T a b l e I I i n d i c a t e that for a r e a s o n a b l y w i d e

of v a p o r flows a n d starting c o n d i t i o n s the c o r r e c t i o n m e t h o d
Table II.
range
proposed
Results for Different Vapor Flows and Starting

Conditions for Sample Problems
Condenser
Reboiler
Vapor
hi
Vu
Vl
Number of
Iterations to
Converge
210
270
210
210
220
210
.5
.8
.8
.1
.4
.4
270
330
275
275
300
275
1.5
1.5
1.0
1.5
1.0
1.0
10
17
Diverge
10
Diverge
Temp
of
converge.
Vapor
Flow
Temp.
Flow
This is run reported in Table I.

134
EXTRACTIVE
AND
AZEOTROPIC
DISTILLATION
h e r e w i l l g i v e a g o o d s o l u t i o n for this p r o b l e m . T h e system s t u d i e d s h o u l d

b e a g o o d test because i t is h i g h l y n o n i d e a l . A n i n d i c a t i o n of this is t h a t
t e m p e r a t u r e a n d c o m p o s i t i o n m a x i m a a n d m i n i m a w e r e f o u n d for most
p r o b l e m s w h e n these v a r i a b l e s w e r e p l o t t e d against stage n u m b e r .
M a n y v a r i a t i o n s of the c o r r e c t i o n m e t h o d w e h a v e p r o p o s e d c a n be
u s e d . A m o n g these are the use of the same J a c o b i a n for several iterations
a n d t h e use of m o d i f i e d N e w t o n m e t h o d s s u c h as M a r q u a r d t ' s
(S).
We
h a v e t r i e d M a r q u a r d t ' s m e t h o d o n some of these
method
problems
w i t h o u t o b s e r v i n g a n y significant i m p r o v e m e n t , b u t this is o n l y a tentative

evaluation.
I m p r o v e d m e t h o d s for g e n e r a t i n g s t a r t i n g c o n d i t i o n s w o u l d
be helpful.
A c o m p a r i s o n of the m e t h o d p r o p o s e d i n this p a p e r w i t h other m e t h
ods is difficult because there are f e w
distillation problems.
p u b l i s h e d solutions for
nonideal
W e w e r e u n a b l e to find a c o m p l e t e l y s o l v e d p r o b
l e m w i t h a l l m a t e r i a l a n d energy balances satisfied.
We
have
demon
strated that the J a c o b i a n m a t r i x gives r a p i d c o n v e r g e n c e i n the v i c i n i t y

of t h e s o l u t i o n , a n d this m e t h o d m i g h t serve as a basis to e v a l u a t e other
methods.
Acknowledgment
T h e authors w i s h to a c k n o w l e d g e
the assistance of the
Computer
C e n t e r at the U n i v e r s i t y of P i t t s b u r g h .
List of
Symbols
G e n e r a l : A l o w e r case s y m b o l is a scalar. A n u p p e r case s y m b o l is

a c o l u m n vector. A n u p p e r case s y m b o l w i t h a s u p e r s c r i p t is a c o l u m n
v e c t o r f o r m e d b y r e m o v i n g the c o l u m n i n d i c a t e d b y t h e s u p e r s c r i p t
f r o m t h e m a t r i x w i t h the same name. U n d e r l i n e d u p p e r case s y m b o l s
are matrices. I f a s y m b o l is defined as a v e c t o r t h e n w h e n u n d e r l i n e d ,
i t represents a d i a g o n a l m a t r i x w i t h the same elements as the vector.
A m a t r i x w i t h a s u p e r s c r i p t is a l w a y s a d i a g o n a l m a t r i x .
A
C
D
F
G
H
V a p o r d i s t r i b u t i o n m a t r i x : au = 1, ^ = f r a c t i o n of t o t a l v a p o r
l e a v i n g stage / w h i c h goes to stage i
L i q u i d d i s t r i b u t i o n m a t r i x : b = 1, by = f r a c t i o n of t o t a l l i q u i d
l e a v i n g stage / w h i c h goes to stage i
T h e d i r e c t s u m of the i n d e p e n d e n t v a r i a b l e s , ( V,X ,...
X ,T)
T h e d i r e c t s u m of t h e error vectors, ( E , . .
E )
E r r o r m a t r i x , the c o l u m n s are defined b y E q u a t i o n s 12 a n d 13
F e e d m a t r i x : fa is t o t a l f e e d of c o m p o n e n t / to stage i , mass p e r
unit time
V a p o r e n t h a l p y vector; gi is specific e n t h a l p y of v a p o r i n stage i,
energy p e r u n i t mass
L i q u i d e n t h a l p y vector; hi is specific e n t h a l p y of l i q u i d i n stage i,
e n e r g y p e r u n i t mass
u
m+1

8.
B R U N O ,
I
J
YANOSIK,
A N D
T I E R N E Y
Nonideal
135
Mixtures
T h e identity matrix
T h e J a c o b i a n m a t r i x ; i t is p a r t i t i o n e d i n t o ( r a + l ) s u b m a t r i c e s ,
e a c h of size b y n. ]
is t h e s u b m a t r i x i n r o w k a n d c o l u m n ; o f
the p a r t i t i o n e d m a t r i x .
L i q u i d flow rate vector; l is t o t a l l i q u i d l e a v i n g stage i, mass p e r
unit time
N u m b e r of components
N u m b e r of e q u i l i b r i u m stages
H e a t exchange vector; q is rate at w h i c h e n e r g y is a d d e d to stage
i b y heat exchange, energy p e r u n i t t i m e
F e e d e n t h a l p y vector; q is e n t h a l p y of f e e d e n t e r i n g stage i, e n e r g y
per unit time
D e f i n e d as B A ; R A B
T e m p e r a t u r e vector; t is t e m p e r a t u r e i n stage i
A vector e a c h element of w h i c h is 1.0
V a p o r flow rate vector; t>< is t h e t o t a l v a p o r l e a v i n g stage i, mass
per unit time
L i q u i d c o m p o s i t i o n m a t r i x ; xy is c o m p o s i t i o n of c o m p o n e n t / i n
l i q u i d i n stage i
V a p o r composition matrix;
is c o m p o s i t i o n of c o m p o n e n t / i n
v a p o r i n stage i
A c t i v i t y coefficient m a t r i x f o r t h e l i q u i d p h a s e ; t h e ij element is t h e
a c t i v i t y coefficient f o r c o m p o n e n t / i n stage i
E q u a l t o z e r o w h e n k ^ /; e q u a l to 1.0 w h e n k /
A c t i v i t y coefficient m a t r i x f o r v a p o r p h a s e ; t h e ij element is a c t i v i t y
coefficient f o r c o m p o n e n t ; i n stage i
S u b s c r i p t u s e d to i n d i c a t e i t e r a t i o n n u m b e r
E u c l i d e a n n o r m of c o m p o s i t i o n errors, E q u a t i o n 3 3
E u c l i d e a n n o r m o f energy b a l a n c e errors, E q u a t i o n 34
2
kj
Q
Q
U
V
X
Y
Sjcj
t i
_ 1
_ 1
Literature Cited
1. Tierney, J. W., Bruno, J. ., "Equilibrium Stage Calculations," AIChE J.
(1967) 13, 556.
2. Tierney, J. W., Yanosik, J. L., "Simultaneous Flow and Temperature Correc
tions in the Equilibrium Stage Problem," AIChE J. (1969) 15, 897.
3. Tierney, J. W., Yanosik, J. L., Bruno, J. ., "Solution of Equilibrium Stage
Models for Solvent Extraction Processes," Proceedings International Sol
vent Extraction Conference 1971, pp. 1051-1061, Society of Chemical
Industry, London, 1971.
4. Roche, E. C., "Rigorous Solution of Multicomponent, Multistage LiquidLiquid Extraction Problems," Brit. Chem. Eng. (1969) 14, 1393.
5. Nelson, P. ., "Countercurrent Equilibrium Stage Separation with Reaction,"
AIChE J. (1971) 17, 1043.
6. Oliver, E. D., "Diffusional Separation Processes," pp. 189-197, Wiley, New
York, 1966.
7. Drickamer, H. G., Brown, G. G., White, R. R., Trans. AIChE J. (1945) 41,
555.
8. Marquardt, D. W., "An Algorithm for Least-Squares Estimation of Non
linear Parameters,"J.Soc. Ind. Appl. Math. (June 1963) 2, 431.
RECEIVED December 10, 1971.
9
Isobaric Vapor-Liquid Equilibrium in the
Acetic Acid-Acetone System
R. JOE BURKHEAD and J. THOMAS SCHRODT
University of Kentucky, Lexington, Ky. 40506
Isobaric vapor-liquid equilibrium data for the system acetic

acid-acetone have been obtained at 760 and 500 mm Hg,
using an Altsheler still Acetic acid associates in the liquid
and vapor phases, and this is accounted for in evaluating
modified activity coefficients for the components. This system primarily shows small negative deviations of the coefficients with a maximum and a minimum appearing at high
acetone mole fractions for both pressures. In evaluating the
thermodynamic consistency of the data, the Herington test
for isobaric data gave values of D J of 5.4 and 7.6 at 760
and 500 mm Hg, respectively. The Redlich-Kister integral
area method with an estimate of the heat of mixing term
gave areas of 0.023 and 0.025 at 760 and 500 mm Hg,
respectively.
/ C o n s i s t e n t v a p o r - l i q u i d e q u i l i b r i u m d a t a are necessary to d e s i g n a l l
^
types o f r e c t i f i c a t i o n devices. H o w e v e r , m a n y i n d u s t r i a l l y i m p o r t a n t
m i x t u r e s are n o n i d e a l , p a r t i c u l a r l y i n the l i q u i d phase, a n d p r e d i c t i n g t h e i r

e q u i l i b r i u m p r o p e r t i e s f r o m f u n d a m e n t a l t h e r m o d y n a m i c s is not possible.
T h u s , the c o r r e l a t i n g o f e x p e r i m e n t a l x-y-t
a n d x-y-P
d a t a has d e v e l o p e d
as a n i m p o r t a n t b r a n c h of a p p l i e d t h e r m o d y n a m i c s .
T h e n o n i d e a l i t i e s o f e q u i l i b r i u m m i x t u r e s result f r o m v a r i o u s c o m b i n a t i o n s of m o l e c u l a r interactions; o n e s u c h i n t e r a c t i o n that has
been
r e c e n t l y s t u d i e d is m o l e c u l a r association. M o l e c u l e s of fatty acids s u c h

as acetic a c i d t y p i c a l l y f o r m d i m e r s a n d , to a lesser extent, t r i m e r s b y
h y d r o g e n b o n d i n g i n the v a p o r a n d l i q u i d states. F a i l u r e of the e q u i l i b r i u m d a t a o f b i n a r y systems c o n t a i n i n g a c e t i c a c i d to m e e t e s t a b l i s h e d
c r i t e r i a o f consistency b a s e d u p o n the G i b b s - D u h e m r e l a t i o n has
o b s e r v e d b y R i u s et al. (1),
C a m p b e l l et al. (2),
been
Herington (3), and
136

9.
BURKHEAD
M a r e k (4).
AND
Acetic
SCHRODT
Acid-Acetone
H e r e w e t r y to o b t a i n x-y-t
System
137
d a t a for t h e acetic a c i d - a c e t o n e
system at 760 a n d 500 m m H g a n d to s h o w h o w c o n s i d e r i n g a c i d d i m e r i z a t i o n i m p r o v e s the results for t h e r m o d y n a m i c consistency tests.

Equilibrium
Theory
T h e l i q u i d phase a c t i v i t y coefficient of a c o m p o n e n t i n a L V m i x t u r e
is u s u a l l y g i v e n b y
T,
Pf
(D
w h e r e 0* is the i m p e r f e c t i o n pressure c o r r e c t i o n f a c t o r a n d the absent

v a p o r p h a s e a c t i v i t y coefficient is t a k e n as u n i t y . I n systems c o n t a i n i n g
a dimerizing component
E q u a t i o n 1 w i l l not g i v e t h e r m o d y n a m i c a l l y
consistent y/s. C o n s i d e r for s u c h a c o m p o n e n t i n a b i n a r y m i x t u r e , t h e

respective m o d i f i e d v a p o r a n d l i q u i d e q u i l i b r i u m expressions,
(2)
k =
(3)
and
w h e r e a n d c represent true m o l e fractions a n d t h e s u b s c r i p t s m2 a n d <Z2,

the m o n o m e r a n d d i m e r , respectively.
F o r the p u r e c o m p o n e n t E q u a t i o n 2 is w r i t t e n as
T)
o2
A s i n a n y t w o phase b i n a r y system, c o n s i d e r i n g the m o n o m e r a n d d i m e r

as t h e t w o c o m p o n e n t s , + =
1 and e
1, w i l l a l l o w E q u a t i o n
e =
d
4 a n d the p u r e c o m p o n e n t f o r m of E q u a t i o n 3 to b e r e d u c e d to
_ V
1 + 42f P
Q
o2
, .
and
1 +4/c - 1
0
2k

(6)
138
T h e a c t i v i t y coefficient
for t h e m o n o m e r
of the p u r e a s s o c i a t i n g c o m
p o n e n t is g i v e n b y
Po2
Y-
TQ m
(n\
(7)
a n d i n t h e presence of a n o n a s s o c i a t i n g c o m p o n e n t b y
(8)
,2
= P)m2
m32
Tm2
C o m b i n i n g E q u a t i o n s 4, 5, 6, a n d 7 a n expression for t h e h y p o t h e t i c a l
s a t u r a t i o n v a p o r pressure of the p u r e m o n o m e r is o b t a i n e d :
jy
i
m =
Omko
1 + 4Ko?o2 ~
1 +
7 = = =
YmAo
4k
/ x
T h e s t o i c h i o m e t r i c m o l e fractions of t h e associating c o m p o n e n t
given
1
are
by
yt
= 7
^2
(10)
2 < ; 2
and
m2 +
jr
1 +
2e
/-,-,
u t ;
d 2
<*2
T h e s e g i v e w i t h E q u a t i o n s 2 a n d 3, r e s p e c t i v e l y ,
"
2/2
1 +
4UL
2jfp
(2-2/ )
2
(2-y0
y i
/iox
( 1 2 )
and
V
1 + 4k x ( 2 - x ) 2k x, ( 2 - x )
2
1 Q
( 1 3 )
I f E q u a t i o n s 9, 12, a n d 13 are s u b s t i t u t e d i n t o E q u a t i o n 8, a m o d i f i e d
e q u i l i b r i u m r e l a t i o n c o n t a i n i n g v a p o r a n d l i q u i d associations factors
and
results:
2/ =
2

(14)
9.
B U R K H E A D
Acetic Acid-Acetone
A N D SCHRODT
System
139
where
1 +
1 +
4K
1 +
1 +
4 t f 2/ (2-2/ )
2
and
i +
1 +
1 +
+
4ifc z
(2-z )
F o r a nonassociating component, B , i n the mixture, the true m o l e

fractions a r e r e l a t e d t o t h e s t o i c h i o m e t r i c m o l e fractions b y
xi
T-r
and
(18)
T h e s e a r e c o m b i n e d w i t h E q u a t i o n s 2, 3, 10, a n d 11 to o b t a i n e q u a t i o n s
for t h e t r u e m o l e fractions o f 1 i n t h e v a p o r a n d l i q u i d phases, respec
tively:
yi
1 +
*K
- V 1 + AK y (2-y )
2K P(2-y y
P(2-2/ )
(19)
and
1 +
4fc(2-s ) 2
1 +
4fc s
(2- )
X i
.
)
A m o d i f i e d e q u i l i b r i u m r e l a t i o n f o r c o m p o n e n t 1 is w r i t t e n i n terms o f
a n d
c o r r e c t i o n factors f o r t h e a s s o c i a t i o n o f A i n t h e v a p o r a n d
l i q u i d phases, b y c o m b i n i n g E q u a t i o n s 8 ( w r i t t e n f o r c o m p o n e n t
1),
19, a n d 2 0 :
! = r
L T L
X!Poi
(21)
where
z
2
y + V 1 + 4K y {2-y ))
(2-y ) (1 + V 1 + 4K y , ( 2 - y , ) )
2

140
EXTRACTIVE
AND
AZEOTROPIC
DISTILLATION
and
2 (l-x
(2-x )
2
(1 +
1 +
4fc
1 +
4fc ( 2 - ) )
x {2-x ))
2
(23)
T h e p r e c e d i n g d e r i v a t i o n s are g i v e n i n m o r e d e t a i l b y M a r e k a n d
S t a n d a r t ( 5 ) a n d are a p p l i e d b y M a r e k (4)
to several b i n a r y systems.
T h e terms a n d 0 a r e e v a l u a t e d f r o m p a r t i a l m o l a l v o l u m e d a t a o r
2
a p p r o x i m a t e d f r o m g e n e r a l i z e d correlations.
A c c o r d i n g to M a r e k a n d
Standart, t h e p r o d u c t s a n d m u s t satisfy a l l c r i t e r i a o f t h e r m o
2
d y n a m i c consistency, as s h o u l d a n d y f o r nonassociating systems.

2
T o evaluate t h e a c t i v i t y coefficients, IYy*, o f a L - V system c o n t a i n i n g

a n associating c o m p o n e n t , t h e o n l y other d a t a n e e d e d a r e t h e m o d i f i e d
v a p o r phase association constants, K a n d K. T h e s e are a f u n c t i o n of t e m
0
p e r a t u r e a n d pressure, a n d f o r t h e y a r e also a f u n c t i o n o f t h e n o n associating c o m p o n e n t .
V a l u e s of a r e scarce; h o w e v e r , t h e y m a y b e
a p p r o x i m a t e d b y e x t r a p o l a t i n g K d a t a t o temperatures b e l o w t h e n o r m a l
0
b o i l i n g p o i n t of t h e associating c o m p o n e n t .
Modified Redlich-Kister
Test
O n e m e t h o d o f e v a l u a t i n g t h e o v e r a l l t h e r m o d y n a m i c consistency of
b i n a r y , i s o b a r i c L - V e q u i l i b r i u m d a t a is b a s e d o n t h e e q u a t i o n
(24)
T h e greater t h e heats o f m i x i n g a n d differences of b o i l i n g points o f

the c o m p o n e n t s , t h e greater t h e v a l u e o f t h e r h s i n t e g r a l .
I n systems
w h e r e this is true, this q u a n t i t y is e v a l u a t e d to test o v e r a l l consistency.

If x-y-t
d a t a a r e a v a i l a b l e at m o r e t h a n o n e pressure a n d i f t h e
assumption
(25)
is v a l i d , t h e n Ah /R
M
is d e t e r m i n e d as a f u n c t i o n of a n d of b y o b
t a i n i n g values o f Xid In y / d ( l / T ) over a range o f ( 6 ) . T h e s e

4
values a n d E q u a t i o n 24 w i l l test f o r consistency.

Ah /R
M
9.
BURKHEAD
AND
SCHRODT
Acetic
Acid-Acetone
141
System
Experimental
A n A l t s h e l e r s t i l l w a s u s e d t o o b t a i n t h e x-y-t d a t a a t 760 a n d 500
m m H g (see R e f e r e n c e 7 f o r a d e s c r i p t i o n o f this s t i l l ) . A s c h e m a t i c
d i a g r a m o f o u r a p p a r a t u s is g i v e n i n F i g u r e 1.
T h e pressure o f t h e system w a s c o n t r o l l e d t o w i t h i n 0 . 5 m m H g
for e a c h series b y a C a r t e s i a n d i v e r manostat c o n n e c t e d t o a p o s i t i v e a i r
leak, a v a c u u m p u m p , a n d a surge v o l u m e o f 12 liters. A n a b s o l u t e
mercury-in-glass m a n o m e t e r w i t h a 0.1 m m s l i d i n g v e r n i e r w a s u s e d t o
measure t h e pressure. T e m p e r a t u r e s w e r e m o n i t o r e d via t w o c o p p e r c o n s t a n t a n t h e r m o c o u p l e s ; o n e w a s l o c a t e d just a b o v e t h e l i q u i d surface
a n d the other just b e l o w it. M a x i m u m diffrences o f 0.4C w e r e detected,
b u t a n average o f t h e t w o r e a d i n g s w a s r e p o r t e d t o 0.2C. G l a c i a l acetic
a c i d a n d acetone, b o t h m e e t i n g A C S specifications, w e r e u s e d .
T o b e g i n a r u n , t h e s t i l l w a s c h a r g e d w i t h 500 m l o f s o l u t i o n a n d
a l l o w e d to b o i l for 3 - 4 h o u r s ; e q u i l i b r i u m w a s assured b y a constant b o i l i n g t e m p e r a t u r e f o r a t least one h o u r . F o r the series a t 500 m m H g , i c e
w a t e r w a s c i r c u l a t e d t h r o u g h t h e condenser to m i n i m i z e v a p o r losses.
S a m p l e s w e r e w i t h d r a w n a t t h e system o p e r a t i n g pressure, a n d t h e i r
densities d e t e r m i n e d a t 2 5 0.1C. T h e c o m p o s i t i o n w a s a n a l y z e d b y
this m e t h o d because o f the l a r g e difference i n densities o f t h e t w o c o m ponents; measurements accurate t o 0 . 2 m o l e % w e r e r e c o r d e d .
Condenser
_Air
Leak
Drying Tube
Ice-Water
Bath
Surge Bottles
rtr
Manostat
Variac
Transformer
Liquid Phase
Sampling Flasks
Vacuum
Water
Pump
Manometer
Absolute
Mercury
Manometer
-Vapor Phase Sampling Flask

Figure 1.
Results
and
Schematic diagram of experimental
apparatus
Discussion
T h e x-y-t d a t a f o r the acetic a c i d - a c e t o n e system at 760 a n d 500 m m

H g are presented i n F i g u r e 2 a l o n g w i t h the d a t a of Y o r k a n d H o l m e s ( 8 )
at 760 m m H g . V a l u e s o f the s t a n d a r d a c t i v i t y coefficients, y f o r acetone

142
E X T R A C T I V E
120 r
A N DA Z E O T R O P I C
DISTILLATION
Mole Fraction Acetone

Figure 2.
Isobaric equilibrium
data of acetic
acid-acetone
a n d f o r a c e t i c a c i d , w e r e c a l c u l a t e d u s i n g : E q u a t i o n 1, s m o o t h e d d a t a
2
f r o m F i g u r e 2, t h e A n t o i n e v a p o r pressure e q u a t i o n f o r acetone ( 9 ) ,
e x p e r i m e n t a l v a p o r pressure d a t a f o r a c e t i c a c i d (10, 11, 12), a n d a t a b l e
of i m p e r f e c t i o n pressure c o r r e c t i o n factors (13).
0
Figure 3.
0.1
Activity
T h e s e y's are p r e s e n t e d
0.2 0.3
0.4 0.5 0.6 0.7 0.8
Mole Fraction Acetone in Liquid phase
coefficients
of acetic acid-acetone
0.9
at 760 mm Hg

1.0
9.
BURKHEAD
AND
Acetic Acid-Acetone System
SCHRODT
143
as a f u n c t i o n o f i n F i g u r e s 3 a n d 4. B o t h sets o f curves s h o w p o s i t i v e
a n d n e g a t i v e d e v i a t i o n s f r o m i d e a l i t y a n d a m a x i m u m a t = 0.24. Iso
b a r i c e q u i l i b r i u m studies b y R i u s et al. (1) o f acetic a c i d a n d l o w m o
l e c u l a r w e i g h t a l c o h o l b i n a r y solutions r e s u l t e d i n s i m i l a r l y s h a p e d curves.
F i r s t , t h e d a t a seem t o b e inconsistent since the m a x i m a at x = 0.24 a r e
x
not b a l a n c e d b y m i n i m a a t t h e same c o m p o s i t i o n .
I n c l u d i n g t h e heat o f
m i x i n g t e r m t h a t is necessary f o r i s o b a r i c d a t a d i d not c o n f i r m consistency.

T o i n c l u d e t h e effect o f t h e association o f t h e a c i d , t h e m o d i f i e d a c t i v i t y
coefficients, a n d , w e r e e v a l u a t e d .
2
0.25 j
0.1
Figure 4.
1 1
1 1
1 1
1 1 1 1 1 1
0.2 0.3 0.4 0.5 0.6 0.7 0.8

Mole Fraction Acetone in Liquid Phase
0.9 1.0
Activity coefficients of acetic acid-acetone at 500 mm Hg
T o c a l c u l a t e Z a n d a p p e a r i n g i n E q u a t i o n s 14 a n d 2 1 , f r o m E q u a
2
tions 15 a n d 22, M a r e k ' s e q u a t i o n f o r K (4)

0
-log
K >^
0{1
a n d e x p e r i m e n t a l values o f K
temperature
Ko(pô) a n d
a n d pressure.
= 10.4205 -
0)
(26)
(14, 15) w e r e p l o t t e d as a f u n c t i o n o f
Differences
b e t w e e n t h e values
of log
t h e e x p e r i m e n t a l values o f l o g K at t h e same t e m p e r a t u r e
0
w e r e t h e n p l o t t e d as a f u n c t i o n o f t e m p e r a t u r e a n d pressure, a n d isobars
through the points were extrapolated
to the e q u i l i b r i u m
temperatures.
A d d i t i o n o f c o r r e s p o n d i n g l o g K a n d l o g K0(P-*0) f r o m E q u a t i o n 2 6
0
gave
- l o g i f = 1.4040 l o g o2 -
1.8821

(27)
144
EXTRACTIVE
AND AZEOTROPIC
DISTILLATION
T o d e t e r m i n e K, the association constant o f acetic a c i d i n t h e m i x t u r e ,

t h e a p p r o p r i a t e isobars, 760 a n d 500 m m H g , w e r e e x t r a p o l a t e d t o t e m
peratures b e l o w t h e b o i l i n g p o i n t . T h e equations o b t a i n e d for w e r e
-log
= 9.9905 + 0.00224* -
7 6 0 )
( >
28
and
- l o g # 5oo) = 10.0505 + 0.00209* (
(29)
T h e e x p e r i m e n t a l d a t a u s e d t o d e t e r m i n e these constants w e r e scant, a n d

t h e i r q u a l i t y is d e b a t e d r e g a r d i n g t h e i r u s e f o r these d e t e r m i n a t i o n s .
F o r m u l a t i o n o f l o g K vs. a t constant pressure as a l i n e a r f u n c t i o n is
0
n o t necessarily c o r r e c t a n d w a s d o n e for l a c k o f another m e t h o d . V a l u e s o f

Z
a n d , c a l c u l a t e d u s i n g E q u a t i o n s 15 a n d 23, w e r e u s e d i n E q u a t i o n s
14 a n d 21 to e v a l u a t e a n d .
2
F i g u r e s 3 a n d 4 also s h o w the curves o f In a n d In vs. x

2
i9
and
t h e a p p e a r a n c e o f these curves i m p r o v e i m m e d i a t e l y b y c o n s i d e r i n g t h e
association i n c a l c u l a t i n g these m o d i f i e d a c t i v i t y coefficients.
T h e s e plots
s h o w t w o u n u s u a l f e a t u r e s n e g a t i v e deviations i n t h e a c t i v i t y coefficients
a n d a m a x i m u m - m i n i m u m set a t h i g h m o l e f r a c t i o n acetone.
N e g a t i v e deviations s h o w e d b y b o t h sets o f datai.e., values o f
less t h a n o n e a r e c h a r a c t e r i s t i c o f electrolytes o r o f m i x t u r e s i n w h i c h
association o r c o m p o u n d f o r m a t i o n b e t w e e n the t w o c o m p o n e n t s reduces
0.20 r \
1 1 1 1 11 11 1
11r

Figure 5.
Thermodynamic consistency plot for acetic acid-acetone system

at 760 mm Hg

9.
B U R K H E A D
Acetic Acid-Acetone
A N D SCHRODT
145
System
0.20 r 1
_0 inL
0
Figure 6.
0.1

0.2
0.3
0.4
0.5
0.6
0.7
0.8
0.9
1.0
Thermodynamic consistency plot for acetic acid-acetone system

at 500 mm H g
t h e i r v o l a t i l i t y . T h u s , i t seems that there is a s s o c i a t i o n o r a t t r a c t i o n b e

t w e e n t h e a c e t i c a c i d a n d acetone m o l e c u l e s i n t h e l i q u i d , besides t h e
acetic a c i d d i m e r i z a t i o n .
A m a x i m u m a n d m i n i m u m a r e o b s e r v e d i n t h e curves o f In a n d
In T j2 f o r b o t h sets o f d a t a . I n b o t h d a t a sets these o c c u r at x

2
about
e q u a l t o 0.65. T h e values o f a r e s l i g h t l y greater a t 760 m m H g t h a n

at 500 m m H g t h r o u g h o u t t h e range o f c o m p o s i t i o n s . N o other significant
differences a r e n o t e d b e t w e e n t h e t w o sets o f curves.
F r o m t h e plots o f In ( 2 / ) vs. , s h o w n i n F i g u r e s 5 a n d 6
2
for t h e t w o sets o f d a t a , values f o r t h e H e r i n g t o n test c a l c u l a t i o n s w e r e

determined.
A c c o r d i n g t o H e r i n g t o n ( 3 ) , D J m u s t b e less t h a n 10
i f t h e d a t a a r e consistent. A t 760 m m H g pressure, D is 33.6, a n d / is 28.2,

giving D -
J = 5.4. A t 5 0 0 m m H g pressure, D =
36.4 a n d / = 28.8,
g i v i n g D J= 7.6. T h u s b o t h sets o f d a t a seem t o b e t h e r m o d y n a m i c a l l y

consistent b a s e d o n this test.
F r o m F i g u r e s 5 a n d 6, t h e R e d l i c h - K i s t e r test a p p a r e n t l y w i l l n o t
suffice f o r this system since t h e i n t e g r a t e d areas o f t h e curves a r e n o t
zero.
R e t a i n i n g E q u a t i o n 24, v a l u e s o f A r V V R T
were calculated using
the p r o c e d u r e o u t l i n e d a b o v e . T h e results a r e p r e s e n t e d i n T a b l e I, a l o n g
w i t h values o f
1
j
In ( , tt/Tx ) dx

146
Table I.
DISTILLATION
Modified Redlich-Kister Consistency Test Results
1
P ,mmHg
@ = 0
In ^
J O
760
500
AZEOTROPIC
dxi
-0.0234
- 0.0244
/
J T @ X
l ^ d T
1
Area
-0.0465
- 0.0492
0.0231
0.0248
as d e t e r m i n e d f r o m F i g u r e s 5 a n d 6. A l t h o u g h t h e differences
between
these values seem r a t h e r large, s t u d y i n g t h e p r o c e d u r e s u s e d i n e v a l u a t i n g

In ( / ) a n d Ah /R
2
i n d i c a t e s t h a t t h e difference
b e t w e e n these
values is w e l l w i t h i n t h e l i m i t s o f t h e e x p e r i m e n t a l a n d p r o c e d u r a l errors.
O n e difficulty i n e v a l u a t i n g these q u a n t i t i e s is t h e relative smallness of
t h e d e v i a t i o n s f o r this system as c o m p a r e d w i t h m a n y other systems.
V a l u e s of In close to z e r o t h r o u g h o u t t h e c o m p o s i t i o n r a n g e cause
s l i g h t errors i n t h e system parameters t o b e significant i n t h e a r e a deter
m i n a t i o n s . P r i m a r i l y i m p o r t a n t for i s o b a r i c systems is t h e fact t h a t t h e
heat o f m i x i n g t e r m i n t h e equations d e r i v e d f r o m t h e b a s i c G i b b s - D u h e m
relationship cannot be ignored a n d must b e calculated to indicate the
d a t a consistency. W i t h i n t h e l i m i t s of e x p e r i m e n t a l error, t h e m o d i f i e d
R e d l i c h - K i s t e r test i n d i c a t e s m a r g i n a l consistency of o u r d a t a .
Acknowledgment
G r a t e f u l a c k n o w l e d g m e n t is m a d e to t h e A s h l a n d O i l a n d R e f i n i n g
C o . for s u p p o r t i n g this w o r k w i t h a f e l l o w s h i p .
List
of
D
Ak
J
H e r i n g t o n test p a r a m e t e r
heat o f m i x i n g
H e r i n g t o n test p a r a m e t e r
v a p o r p h a s e association e q u i l i b r i u m constant
l i q u i d p h a s e association e q u i l i b r i u m constant
t o t a l pressure
gas constant
absolute t e m p e r a t u r e
temperature
s t o i c h i o m e t r i c l i q u i d m o l e fractions
s t o i c h i o m e t r i c v a p o r m o l e fractions
v a p o r phase association constant
l i q u i d p h a s e association constant
a c t i v i t y coefficient
true mole fraction i n l i q u i d
true mole fraction i n vapor
i m p e r f e c t i o n pressure c o r r e c t i o n factor
31
Symbols

9.
B U R K H E A D A N D SCHRODT
Acetic
Acid-Acetone
System
147
Superscripts
L
V
l i q u i d phase
vapor phase
Subscripts
d dimer
m monomer
pure component
1 nonassociating component
2 associating c o m p o n e n t
Literature Cited
1. Rius, ., Otero, J. L., Macorron, ., Chem. Eng. Sci. (1959) 10, 105.
2. Campbell, A. N., Kartzmark, E. M., Gieskes, T. M. T. M., Can. J. Chem.
(1963) 41,407.
3. Herington, E. F. G.,J.Inst. Petrol. (1951) 37, 457.
4. Marek, J., Collection Czech. Chem. Commun. (1955) 20, 1490.
5. Marek, J., Standart, G., ibid. (1954) 19, 1074.
6. Null, H. R., "Phase Equilibrium in Process Design," McGraw-Hill, New
York, 1970.
7. Altsheler, W. B., Ind. Eng. Chem. (1951) 43, 2559.
8. York, R., Holmes, R., Ind. Eng. Chem. (1942) 34, 345.
9. Lange, . ., Ed., "Handbook of Chemistry," Rev. 10th ed., McGraw-Hill,
New York, 1967.
10. MacDougall, J., Smith, H.,J.Amer. Chem. Soc. (1936) 58, 2585.
11. Ramsay, G., Young, R.,J.Chem. Soc. (1886) 49, 790.
12. Weast, R. C., Ed., "Handbook of Chemistry and Physics," 50th ed., The
Chemical Rubber Company, Cleveland, 1970.
13. Burkhead, R. J., M.S. Thesis, University of Kentucky, Lexington, 1971.
14. Johnson, E. W., Nash, C. K.,J.Amer. Chem. Soc. (1936) 58, 2585.
15. Ritter, H. L., Simons, J. H.,J.Amer. Chem. Soc. (1945) 67, 757.
RECEIVED February 10, 1972.

10
Separation of Water, Methyl Ethyl Ketone,
and Tetrahydrofuran Mixtures
HUGH M. LYBARGER and HOWARD L. GREENE
Department of Chemical Engineering, The University of Akron,
Akron, Ohio 44304
Ternary vapor-liquid equilibrium data for the system

water-methyl ethyl ketone-tetrahydrofuran were determined with a vapor recirculating equilibrium still of the
type used by Hipkin and Myers. All experimental points
were checked for thermodynamic consistency using the test
proposed by McDermott and Ellis. Calculated liquid phase
activity coefficients were correlated over the range of solvent
concentrations using regression analysis. These results indicate a low boiling valley between the binary azeotropes of
water-tetrahydrofuran and water-methyl ethyl ketone, but
no ternary azeotrope was found. A solvent purification
scheme, aided by development of a modified Thiele-Geddes
computer program, was designed to separate the ternary
mixture into pure components. The resulting system requires use of three ordinary distillation columns and extractive distillation, using dimethylformamide as the solvent.
'êfrahydrofuran
( T H F ) a n d m e t h y l e t h y l k e t o n e ( M E K ) are c o m -
m o n l y u s e d as solvents for h i g h m o l e c u l a r w e i g h t p o l y v i n y l c h l o r i d e
resins i n t o p c o a t i n g a n d a d h e s i v e a p p l i c a t i o n s . B l e n d s are u s e d to c o m b i n e the l o w cost o f m e t h y l e t h y l ketone w i t h the h i g h e r s o l v e n c y a n d
greater v o l a t i l i t y of t e t r a h y d r o f u r a n .
B e c a u s e of the large a m o u n t of
T H F u s e d , its r e l a t i v e l y h i g h cost, a n d a i r p o l l u t i o n considerations, rec o v e r y is n o r m a l l y necessary.

T h e solvent v a p o r m a y b e r e c o v e r e d i n c o m m e r c i a l l y a v a i l a b l e activ a t e d c a r b o n a d s o r p t i o n units.
W h e n the v a p o r - a i r m i x t u r e is passed
t h r o u g h a b e d of a c t i v a t e d c a r b o n , solvent vapors are a d s o r b e d w h i l e

the s t r i p p e d a i r passes t h r o u g h . P e r i o d i c regeneration o f the a c t i v a t e d
148

10.
LYBARGER
AND
GREENE
Separation
of
149
Mixtures
c a r b o n w i t h l o w pressure steam, h o w e v e r , g e n e r a l l y contaminates t h e

solvents w i t h a large a m o u n t o f w a t e r , i n c r e a s i n g greatly t h e difficulty of
s u b s e q u e n t separations.
T h i s s t u d y w a s u n d e r t a k e n to o b t a i n t h e necessary v a p o r - l i q u i d
equilibrium
d a t a a n d to d e t e r m i n e
the distillation requirements
r e c o v e r i n g solvent f o r reuse f r o m t h e s o l v e n t - w a t e r
f r o m a d s o r b e r regeneration.
d a t a (2, 3)
for
mixture obtained
Previous binary v a p o r - l i q u i d e q u i l i b r i u m
i n d i c a t e d t w o b i n a r y azeotropes
M E K ) a n d a t w o phase region ( w a t e r - M E K ) .
(water-THF
and water-
T h e t e r n a r y system w a s
thus e x p e c t e d t o b e h i g h l y n o n i d e a l .
Results of this s t u d y h a v e b e e n u s e d to d e s i g n a solvent
recovery
system c a p a b l e of s e p a r a t i n g e a c h solvent i n t o its o r i g i n a l p u r e state. I f

s e p a r a t i o n o f t h e T H F - M E K m i x t u r e is unnecessary o r i f p u r i t y r e q u i r e
ments are less d e m a n d i n g , t h e p r o p o s e d system c o u l d b e a p p r o p r i a t e l y
simplified.
Experimental
A v a p o r - r e c i r c u l a t i n g e q u i l i b r i u m s t i l l s i m i l a r to t h a t d e s c r i b e d b y
H i p k i n a n d M y e r s ( 1 ) w a s u s e d to d e t e r m i n e v a p o r - l i q u i d e q u i l i b r i u m
d a t a f o r t h e system, w a t e r - M E K - T H F . I n this s t i l l s h o w n s c h e m a t i c a l l y
i n F i g u r e 1, a r e c i r c u l a t i n g v a p o r is c o n t i n u o u s l y c o n t a c t e d w i t h a static
l i q u i d sample. T h e v a p o r - l i q u i d system is e n c l o s e d b y a jacket w h e r e
KEY
1
2
3
4
5
7
8
9
I
II
12
13
14
15
16
Figure 1.
Schematic diagram of the equilibrium
Vacuum Pump
Manometer
Mtrcury Traps
Jacket Condenser
Sample Condenser
Thermocouples
Thermistors
Jacket Heater
Reboiler
Jacket
Contactor Body
Contactor Throat
Contactor Sample
Valve
Vapor Sample
Volve
Needle Valves
Nitrogen Tank
still

150
EXTRACTIVE AND AZEOTROPIC
T a b l e I.
Run
No.
ywater.
DISTILLATION
Liquid
YTHF.
Phase
XMEK,
mole fr.
mole fr.
mole fr.
mole fr.
mole fr.
1
3
4
5
6
7
8
910
11
12
13
14
15
16
17
18
19
20
21
22
23
24
25
26
27
28
29"
.288
.217
.256
.257
.275
.236
.199
.226
.297
.244
.226
.234
.267
.314
.250
.247
.121
.103
.230
.163
.248
.311
.269
.244
.215
.181
.206
.262
.181
.289
.177
.209
.388
.223
.102
.178
.478
.216
.058
.162
.327
.299
.182
.174
.039
.278
.619
.123
.477
.599
.291
.304
.040
.350
.284
.284
.532
.494
.566
.534
.337
.541
.699
.596
.225
.540
.717
.604
.407
.387
.568
.580
.841
.619
.152
.714
.275
.090
.440
.452
.746
.474
.510
.453
30
31
32
33
34
35
36
37
38
39
40
41*
.165
.201
.095
.219
.134
.153
.221
.211
.160
.141
.144
.293
.436
.149
.523
.006
.000
.000
.000
.000
.018
.031
.059
.366
.399
.650
.383
.775
.866
.847
.779
.790
.822
.828
.796
.342
42
.353
.370
.277
43
44"
.197
.318
.071
.447
.732
.235
.561
.486
.866
.506
.377
.460
.322
.697
.375
.508
.585
.869
.379
.507
.507
.438
.071
.043
.110
.118
.184
.281
.438
.289
.296
.501
.169
.594
.862
.093
.189
.034
.596
.091
.121
.424
.661
.131
.093
.113
.502
.892
.469
.914
.177
.518
.862
.166
.237
.039
.181
.399
.211
.124
.092
.486
.194
.046
.037
.342
.267
.169
.181
.062
.409
.787
.197
.607
.665
.287
.374
.051
.279
.409
.208
.064
.587
.213
.678
.005
.000
.000
.000
.000
.029
.048
.092
.315
.064
.383
.058
.103
.368
.101
Two-phase run.

10.
LYBARGER
Activity
AND
GREENE
Separation
of
Mixtures
Coefficients
XTHF
water
fMEK
THF
.273
.276
.094
.313
.224
.329
.553
.212
.140
.298
.369
.095
.279
.226
.324
.381
.867
.548
.103
.686
.209
.054
.275
.338
.653
.220
.422
.197
.074
.321
.598
.288
.399
.909
.879
.577
.339
.840
.859
.796
.184
.044
.149
.028
.721
.113
.037
Temp.
C.
mole fr.
2.021
1.710
1.343
2.065
2.497
1.925
2.577
1.267
2.608
1.846
1.598
1.088
2.463
2.157
1.876
2.143
7.289
8.396
5.933
5.455
4.274
3.385
2.188
2.994
3.101
1.244
4.588
1.722
1.891
8.008
1.878
1.379
1.612
1.352
3.058
1.353
1.723
2.045
7.152
1.375
1.611
1.661
1.476
1.057
0.980
0.962
0.989
1.050
1.167
1.481
1.186
1.318
1.791
1.060
1.946
1.752
6.582
1.738
1.362
1.587
1.306
2.794
1.421
1.777
2.005
6.462
1.343
1.570
1.706
1.483
1.022
1.041
1.182
1.035
1.136
1.407
1.492
1.242
1.204
1.968
1.173
64.7
65.3
61.6
64.0
67.9
65.8
63.5
64.9
68.8
65.3
63.6
64.2
67.4
67.5
65.5
65.5
62.9
67.4
72.2
64.8
69.6
70.5
67.0
67.1
62.9
67.7
65.7
67.4
5.872
4.179
8.089
1.558
6.745
5.455
2.321
1.375
5.186
6.412
5.343
1.020
1.108
0.966
1.845
0.000
0.000
0.000
0.000
1.054
1.087
1.065
1.099
1.086
1.086
2.038
1.052
1.022
1.465
2.467
1.025
1.010
1.036
68.8
64.7
71.5
63.1
61.4
62.7
62.0
62.7
63.1
63.1
63.5
68.3
68.8
4.738
1.162
1.063
63.1
70.3

152
EXTRACTIVE
AND
AZEOTROPIC
DISTILLATION
h y d r o c a r b o n v a p o r is m a i n t a i n e d at the b o i l i n g t e m p e r a t u r e of the l i q u i d
s a m p l e i n t h e contactor. T h e s t i l l is t h o r o u g h l y i n s u l a t e d so that the
l i q u i d a n d v a p o r i n the c o n t a c t o r are m a i n t a i n e d at a d i a b a t i c c o n d i t i o n s .
S t a n d a r d i z e d p r o c e d u r e s for o b t a i n i n g e q u i l i b r i u m a n d for s a m p l i n g
t h e r e s u l t a n t v a p o r a n d l i q u i d , as o u t l i n e d b y L y b a r g e r ( 7 ) , w e r e f o l l o w e d . A l l v a p o r - l i q u i d e q u i l i b r i u m d a t a w e r e o b t a i n e d at a constant
pressure of 730 m m of m e r c u r y w h i c h w a s a c h i e v e d b y a p p l y i n g v a c u u m
or n i t r o g e n pressure to the s t i l l ( d e p e n d i n g o n a t m o s p h e r i c pressure)
u n t i l the d e s i r e d differential w a s o b t a i n e d . A f t e r the v a p o r was r e c i r c u l a t e d , a constant pressure c o u l d b e m a i n t a i n e d i n the s t i l l w i t h o u t further
adjustments.
A l l l i q u i d a n d v a p o r samples w e r e a n a l y z e d o n a V a r i a n A e r o g r a p h
M o d e l 202-1B t h e r m a l c o n d u c t i v i t y gas c h r o m a t o g r a p h . A 12-foot c o l u m n
p a c k e d w i t h P o r a p a k Q , w h i c h g a v e a c l e a n s e p a r a t i o n for water, was
u s e d , b u t it c a u s e d the peaks for m e t h y l e t h y l ketone a n d t e t r a h y d r o f u r a n
to b e s l i g h t l y m e r g e d .
T h e c h r o m a t o g r a p h w a s c a l i b r a t e d u s i n g 11 solvent b l e n d s of k n o w n
c o m p o s i t i o n s . A r e a c o r r e c t i o n factors w e r e d e t e r m i n e d f r o m the s t a n d a r d
samples, r e l a t i n g w e i g h t f r a c t i o n to a r e a f r a c t i o n . A l l samples w e r e
a n a l y z e d t w i c e , a n d the results w e r e a v e r a g e d . C a l i b r a t i o n of the c h r o m a t o g r a p h w i t h k n o w n w a t e r - M E K - T H F samples i n d i c a t e d accurate
d e t e r m i n a t i o n to w i t h i n 0.002-0.005 m o l e f r a c t i o n , d e p e n d i n g o n
composition.
Results and
Discussion
VaporLiquid Equilibrium Data.
F o r t y - f o u r pairs of v a p o r - l i q u i d
e q u i l i b r i u m d a t a w e r e d e t e r m i n e d for the t e r n a r y system; l i q u i d c o m p o sitions i n the s i n g l e a n d two-phase regions w e r e s t u d i e d . Results of these

runs are s u m m a r i z e d i n T a b l e
I a l o n g w i t h the l i q u i d phase
activity
coefficients a n d b o i l i n g p o i n t s o b t a i n e d at a pressure of 730 m m of mercury.
Tabulated
compositions
are averages of t w o
analyses for
each
sample. C a l c u l a t e d l i q u i d p h a s e a c t i v i t y coefficients are b a s e d o n R a o u l t ' s

and Dalton's laws:
Pi =
Piji
tiPiXi
(1)
a s s u m i n g v a p o r phase i d e a l i t y .
The
v a p o r l i q u i d e q u i l i b r i u m d a t a for the single-phase
r u n s are
g r a p h i c a l l y s h o w n i n F i g u r e 2 w h e r e the two-phase r e g i o n at 60 C
is
also p l o t t e d to i n d i c a t e the extent of p a r t i a l m i s c i b i l i t y at the b o i l i n g

point.
A l i n e connects e a c h p a i r of v a p o r - l i q u i d e q u i l i b r i u m c o m p o s i -
tions.
T e m p e r a t u r e results for the v a p o r - l i q u i d e q u i l i b r i u m d a t a i n d i c a t e
a l o w b o i l i n g v a l l e y c o n n e c t i n g t h e b i n a r y azeotropes of
(66.2
mole
M E K , normal boiling point 73.4C)
and
waterMEK
water-THF

10.
L Y B A R G E R
A N D
Separation
G R E E N E
of
Water
0.00
THF
0.10
0.20
0.30
0.40
0.50
153
Mixtures
KEY
0.60
0.70
0.80
030
100
MEK
Figure 2.
Ternary vapor-liquid
equilibrium
data for the one-phase region at
730 mm mercury absolute pressure with the solubility envelope for 60 C
(81.7 m o l e
T H F , normal boiling point 64.0C).
The
dashed line
s h o w n i n F i g u r e 2 indicates the a p p r o x i m a t e l o c a t i o n of this v a l l e y .

Results for the two-phase r u n s are p l o t t e d i n F i g u r e 3 a l o n g w i t h
the s o l u b i l i t y e n v e l o p e at 60 C .
A l t h o u g h the e q u i l i b r i u m s t i l l w a s n o t
d e s i g n e d for two-phase o p e r a t i o n , it was p o s s i b l e to o b t a i n the necessary

d a t a for this solvent system since t h e v a p o r i n e q u i l i b r i u m w i t h the t w o phase l i q u i d was a l w a y s single-phase w h e n c o n d e n s e d . S e v e r a l two-phase
samples w e r e a n a l y z e d after c o o l i n g h a d o c c u r r e d , a c c o u n t i n g for t h e fact
t h a t the ends of the l i q u i d - l i q u i d tielines i n this r e g i o n d o n o t q u i t e
e x t e n d to the s o l u b i l i t y c u r v e .
E q u i l i b r i u m vapor compositions
corre-
s p o n d i n g to the l i q u i d c o m p o s i t i o n s are also p l o t t e d i n F i g u r e 3 a n d ,

except for R u n 42 w h i c h e x p e r i e n c e d
severe b u m p i n g d u r i n g b o i l i n g ,
f a l l a l o n g a n a l m o s t straight l i n e .
F o r a t e r n a r y system the c o m p o s i t i o n of v a p o r i n e q u i l i b r i u m w i t h
a heterogeneous l i q u i d m i x t u r e c a n b e r e l a t e d to the l i q u i d c o m p o s i t i o n s
b y two relationships (5).
F i r s t , the same v a p o r c o m p o s i t i o n w i l l result
f r o m a n y l i q u i d c o m p o s i t i o n o n a g i v e n l i q u i d - l i q u i d tieline. S e c o n d , a

154
EXTRACTIVE
AND
AZEOTROPIC
DISTILLATION
s m o o t h c u r v e c a n be d r a w n t h r o u g h the v a p o r c o m p o s i t i o n s i n e q u i
l i b r i u m w i t h heterogeneous
liquid
c o m p o s i t i o n s . T h i s c u r v e extends
f r o m the v a p o r i n e q u i l i b r i u m w i t h the b i n a r y heterogeneous azeotrope

to v a p o r i n e q u i l i b r i u m w i t h the h o m o g e n e o u s l i q u i d w h e r e t h e c o m p o
sitions of t h e t w o l i q u i d phases b e c o m e c o i n c i d e n t ( t h e p l a i t p o i n t ) .
W i t h these t w o r e l a t i o n s h i p s , one c a n .closely a p p r o x i m a t e t h e c o m p o s i
t i o n o f v a p o r i n e q u i l i b r i u m w i t h a g i v e n t w o - p h a s e l i q u i d f r o m F i g u r e 3.
Wottr
0.00
0.10
0.20
0.30
0.40
0.50
0.70
O60
030
0.90
THF
1.00
MEK
Figure 3. Ternary vapor-liquid

equilibrium data for the two-phase region at
730 mm mercury absolute pressure with the solubility envelope for 60 C
Thermodynamic
and Ellis (6)
Consistency.
T h e test d e v e l o p e d b y M c D e r m o t t
w a s u s e d to d e t e r m i n e t h e t h e r m o d y n a m i c c o n s i s t e n c y of
the v a p o r - l i q u i d e q u i l i b r i u m d a t a . T h i s test i n v o l v e s c a l c u l a t i o n of the

deviation, ( D
c d
) , b e t w e e n p a i r s of p o i n t s (c, d)
as d e f i n e d b e l o w :
cd
i=l
(x
ic
+ x)
id
(log y id
log y )
ic

(2)
10.
L Y B A R G E R
Separation
A N D G R E E N E
155
of Mioctures
T h i s d e v i a t i o n is d e r i v e d f r o m t h e i s o t h e r m a l - i s o b a r i c f o r m of t h e G i b b s D u h e m e q u a t i o n a n d c a n b e a p p l i e d to i s o b a r i c e q u i l i b r i u m d a t a b y
m i n i m i z i n g t h e c o m p o s i t i o n a n d t e m p e r a t u r e differences b e t w e e n p a i r s
of points. T h i s w a s d o n e b y c h o o s i n g d a t a paths t h r o u g h t h e ternary
e q u i l i b r i u m d i a g r a m so that differences i n c o m p o s i t i o n a n d t e m p e r a t u r e
b e t w e e n pairs o f p o i n t s w e r e m i n i m i z e d . A p o i n t w a s c o n s i d e r e d to b e
inconsistent i f i t d e v i a t e d m o r e t h a n 0.02 w i t h b o t h o f its n e i g h b o r s .
T h i s d e v i a t i o n w a s chosen since i t a p p r o a c h e d t h e a p p r o x i m a t e l i m i t of
t h e d e v i a t i o n c a u s e d b y a n a l y t i c a l i n a c c u r a c y . R u n s 1, 4, 5, 13, 15, 2 3 ,
27, a n d 28 w e r e d e t e r m i n e d to b e inconsistent o n this basis.
Correlation of Liquid Phase Activity Coefficients. F o r a c t i v i t y c o
efficients to b e u s e d i n d i s t i l l a t i o n c a l c u l a t i o n s , t h e y are n o r m a l l y repre
sented as a f u n c t i o n o f c o m p o s i t i o n . H e r e a m u l t i p l e regression c o m p u t e r
p r o g r a m w a s u s e d to d e t e r m i n e t h e coefficients f o r a n e q u a t i o n o f t h e
form
lny.i
= + a&i + a x
0
aaXz
7&2
+ a3 X 3 + a X i +
2
a&ix
a&
(3)
a& x
2
w h e r e x x , a n d x a r e t h e l i q u i d m o l e fractions of water, m e t h y l e t h y l
ketone, a n d t e t r a h y d r o f u r a n , respectively.
l9
T e r m s w e r e d e l e t e d f r o m t h e regression e q u a t i o n u n t i l a n e q u a t i o n
c o n t a i n i n g o n l y terms h a v i n g a confidence l e v e l of greater t h a n 8 0 % to
i m p r o v e fit ( i n terms o f s u m o f squares e r r o r ) w a s o b t a i n e d . Coefficients
(/s) f o r t h e r e s u l t i n g s i m p l i f i e d equations a r e s u m m a r i z e d i n T a b l e I I
w i t h a n estimate o f fit.
Table II.
Regression Analysis Coefficients Used in Equation 3

an
ai
en
a5
-4.5041
2.4778
-0.0426
2.0063
- 0.1641
-0.0017
2.0828
0.1995
W a t e r (1)
( R = 0.996)
MEK
(2)
( R = 0.983)
THF
(3)
( R = 0.997)
a
2.2301
All a{'8 not listed above were determined to be zero.
F o r m i x t u r e s c o n t a i n i n g m o r e t h a n 0.95 m o l e f r a c t i o n o f either w a t e r o r
M E K , respective a c t i v i t y coefficients f o r w a t e r o r M E K a r e r e c o m m e n d e d
to b e chosen as 1.0 rather t h a n t h e v a l u e p r e d i c t e d b y t h e regression
equations since insufficient d a t a i n these regions cause a c t i v i t y coefficients
to d e v i a t e s o m e w h a t f r o m t h e r e q u i r e d t e r m i n a l v a l u e o f u n i t y .

156
EXTRACTIVE
A N DAZEOTROPIC
DISTILLATION
THF
WATER
f~~
IV
20 Plates
WATER
Figure 4.
Feed 5 th
15 Plates
15 Plats
L/D 9
Feed 5 th
Feed *
L/D* 3
L/D3
MEK
Schematic diagram of solvent separation
T e r n a r y Separation B y Distillation.
scheme
T o design a recovery
system,
a s t a r t i n g c o m p o s i t i o n o f 85 m o l e % w a t e r , 7.5 m o l e % t e t r a h y d r o f u r a n ,
a n d 7.5 m o l e % m e t h y l e t h y l k e t o n e w a s chosen. T h i s assumes 1.5 p o u n d s
of steam p e r p o u n d o f solvent are u s e d for r e g e n e r a t i o n a n d a b l e n d o f
e q u a l a m o u n t s o f the solvents for t h e p o l y v i n y l c h l o r i d e processing.
F i g u r e 2 shows b y t h e r e l a t i v e l e n g t h o f t h e c o n n e c t i n g Unes that
i n t h e r e g i o n o f w a t e r - r i c h l i q u i d m i x t u r e s r e c t i f i c a t i o n to p r o d u c e v a p o r s
r i c h i n T H F is easily o b t a i n e d . H o w e v e r , the existence o f a m i n i m u m
b o i l i n g v a l l e y e x t e n d i n g across the d i a g r a m f r o m the T H F - w a t e r b i n a r y
a z e o t r o p e t o t h e M E K - w a t e r b i n a r y azeotrope m a k e s i t i m p o s s i b l e t o
r e m o v e a l l w a t e r f r o m the o v e r h e a d b y a single d i s t i l l a t i o n . T h e
best
that c a n b e d o n e i n t h e i n i t i a l d i s t i l l a t i o n is a n o v e r h e a d p r o d u c t i n the
l o w b o i l i n g valley a n d a bottom product of substantially pure water.
S e v e r a l alternatives exist t o treat f u r t h e r the o v e r h e a d stream. A
s e c o n d d i s t i l l a t i o n , u s i n g t h e o v e r h e a d f r o m t h e i n i t i a l d i s t i l l a t i o n as feed,
w o u l d y i e l d a n o v e r h e a d close t o the T H F - w a t e r b i n a r y a z e o t r o p e a n d
a b o t t o m i n t h e r e g i o n o f the M E K - w a t e r b i n a r y azeotrope.
These
two
streams c o u l d t h e n b e d r i e d b y r e m o v i n g w a t e r p h y s i c a l l y b y m o l e c u l a r

LYBARGER
10.
AND
Separation
GREENE
of
157
Mixtures
sieve o r c a l c i u m c h l o r i d e treatment, e t c . t o y i e l d r e l a t i v e l y p u r e T H F
and M E K .
A s e c o n d alternative, u s i n g o n l y d i s t i l l a t i o n m e t h o d s , is c o n s i d e r e d
here. T h i s m e t h o d , s h o w n s c h e m a t i c a l l y i n F i g u r e 4, involves t r e a t m e n t
of t h e o v e r h e a d f r o m the first c o l u m n ( c o m p o s i t i o n i n t h e l o w b o i l i n g
v a l l e y ) b y a d d i n g to it sufficient d r y T H F to b r i n g t h e n e w f e e d c o m p o s i t i o n across the l o w b o i l i n g v a l l e y . D i s t i l l a t i o n of this n e w f e e d y i e l d s
the T H F - w a t e r azeotrope as o v e r h e a d a n d a b o t t o m c o n s i s t i n g of d r y
M E K or an M E K - T H F mixture. T h i s T H F - w a t e r azeotrope may then
b e d r i e d b y extractive d i s t i l l a t i o n w i t h d i m e t h y l f o r m a m i d e , as has b e e n
p r e v i o u s l y d i s c u s s e d (4).
T h e b o t t o m p r o d u c t , as a n M E K - T H F m i x -
ture, is easily p u r i f i e d b y a n a d d i t i o n a l d i s t i l l a t i o n , b u t w i t h r e g u l a t i o n
of f e e d c o m p o s i t i o n i n t h e p r e v i o u s c o l u m n , this stream m a y b e
made
to a p p r o a c h p u r e M E K , e h m i n a t i n g the n e e d for this s u b s e q u e n t d i s t i l l a t i o n . F i n a l l y , a s m a l l c o l u m n u s e d t o separate the solvent, d i m e t h y l f o r m a m i d e ( D M F ) , f r o m the w a t e r is necessary to c o m p l e t e the separat i o n scheme.
Multicomponent Computer Methods for Sizing Required Columns.
A modified Thiele-Geddes
m e t h o d , p r o g r a m m e d for a n I B M 370-155,
w a s u s e d to p e r f o r m t h e c a l c u l a t i o n s n e e d e d to size e a c h r e q u i r e d c o l u m n . E x p e r i m e n t a l a c t i v i t y coefficient d a t a w e r e u s e d to a l l o w for n o n ideal l i q u i d phase
behavior
while
e n e r g y balances, u s i n g
estimated
e n t h a l p y d a t a , w e r e u s e d to c o r r e c t for non-constant m o l a l overflow.

T h e t a M e t h o d w a s u s e d for convergence, a n d a l l p l a t e efficiencies
The
were
a s s u m e d to b e 1 0 0 % . ( See R e f e r e n c e 7 for a d d i t i o n a l c a l c u l a t i o n a l details

a n d a program listing. )
Table III.
Stream No.
Flow Rate
(moles/hr)
Composition
(mole fraction)
THF
MEK
H0
DMF
2
Column Specifications
3
100 20.0 80.0 34.3 26.8
.075 .374
.075 .369 .002
.850 .258 .998
7.5 21.6
.635 .799 .016

.215 .011 .984
.150 .190
10
15.2
5.2
10.0
.999
.660 .999
.001
.340
.001
.999
Column Specification and Flowsheet. A s c h e m a t i c d i a g r a m of
the
solvent s e p a r a t i o n scheme a n d t h e results of the c o m p u t e r analysis for

e a c h c o l u m n a r e s h o w n i n F i g u r e 4 a n d T a b l e III, respectively.
Feed
p l a t e locations are g i v e n w i t h respect to the b o t t o m of e a c h c o l u m n . P l a t e

158
EXTRACTIVE AND AZEOTROPIC DISTILLATION
requirements for columns III and IV, which contain dimethylformamide,

are based on an extension of a previous design analysis by Shah and
Greene (4).
Literature Cited
1. "Recovery of THF du Pont Tetrahydrofuran," . I. du Pont de Nemours
and Co. (Inc.), Electrochemicals Department, Wilmington.
2. Methyl Ethyl Ketone, Shell Chemical Corporation, Technical Publication
SC: 50-2, New York.
3. Shnitko, V. ., Kogan, V. B., "Liquid-Vapor Equilibrium in the Systems
Tetrahydrofuran-Water and Tetrahydrofuran-Ethylene Glycol and a
Method for Dehydration of Tetrahydrofuran,"J.Appl. Chem. USSR 4 (6)
1236-1242.
4. Shah, C. S., Greene, H. L., "Vapor-Liquid Equilibrium for the Ternary
System Tetrahydrofuran-Water-Dimethylformamide," J. Chem. Eng. Data
15 (3) 408-411.
5. Hala, E., Pick, J., Fried, V., Vilim, O., "Vapor-Liquid Equilibrium," pp.
107-109, Pergamon, 1967.
6. McDermott, C., Ellis, S. R. M., "A Multicomponent Consistency Test,"
Chem. Eng. Sci. (1965) 20, 293-296.
7. Lybarger, . M., "Ternary Vapor-Liquid Equilibrium Data Applied to the
Separation of a Mixture of Water, Methyl Ethyl Ketone, and Tetrahydro
furan," Thesis, The University of Akron (March 1972).
RECEIVED February 14, 1972.

11
Prediction of Vapor Composition in
Isobaric Vapor-Liquid Systems Containing
Salts at Saturation
D. JAQUES and W. F. FURTER
Department of Applied Chemistry, Royal Melbourne Institute of Technology,
Melbourne, Victoria, Australia, and Department of Chemical Engineering,
Royal Military College of Canada, Kingston, Ontario, Canada
A method is described for calculating equilibrium vapor
compositions from boiling point vs. liquid composition data
in ternary systems composed of two liquid components and
a salt added to saturation. The procedure is tested on the
ethanol-water system containing each of a wide range of
inorganic salts at saturation. The results suggest that good
quality --x data will yield y values of comparable
accuracy.
* T * o o b t a i n v a p o r l i q u i d e q u i l i b r i u m d a t a for b i n a r y systems, i t is n o w
w e l l e s t a b l i s h e d that u n d e r
certain circumstances
it can be
more
accurate a n d less t i m e c o n s u m i n g to m e a s u r e the b o i l i n g p o i n t , the t o t a l

pressure, a n d the l i q u i d c o m p o s i t i o n a n d t h e n use the G i b b s - D u h e m
r e l a t i o n s h i p to p r e d i c t v a p o r c o m p o s i t i o n ( I ) r a t h e r t h a n to m e a s u r e it.
T h e d i s a d v a n t a g e is that there is n o w a y o f c h e c k i n g the t h e r m o d y n a m i c
consistency o f the e x p e r i m e n t a l data.
F o r systems c o m p o s e d o f t w o l i q u i d s a n d a salt at saturation, this
p r o c e d u r e is e s p e c i a l l y attractive because there are c o n s i d e r a b l e e x p e r i
m e n t a l difficulties i n o b t a i n i n g accurate x - t / - T - I I d a t a a n d the
process
is m o r e t i m e c o n s u m i n g t h a n i n the absence o f salts.

A p r o c e d u r e is presented w h i c h is b a s e d u p o n B a r k e r s m e t h o d
for c a l c u l a t i n g v a p o r c o m p o s i t i o n s f r o m the
k n o w n temperature
(2)
de
p e n d e n c e o f the v a p o r pressure of the p u r e constituents, w i t h s u i t a b l e

m o d i f i c a t i o n for the presence o f salt, a n d f r o m the d e p e n d e n c e
o f the
b o i l i n g p o i n t o f the m i x t u r e w i t h c o m p o s i t i o n o f the e q u i l i b r i u m l i q u i d
phase.
159
160
EXTRACTIVE
AND AZEOTROPIC DISTILLATION
Procedure
A c o m p u t e r p r o g r a m is u s e d w h i c h m i n i m i z e s 2 ( - )
0
where the
t o t a l pressure is g i v e n b y :
n
= x p '
+ (-)' ,
(1)
U s i n g a n d p ' i n s t e a d o f t h e s a t u r a t i o n v a p o r pressures o f t h e p u r e
2
l i q u i d components
a l l o w s f o r t h e presence
o f salt.
F o r salt-saturated
systems i t i s p r o p o s e d t o base t h e a c t i v i t y coefficients o n a s t a n d a r d state

of e a c h l i q u i d c o m p o n e n t s a t u r a t e d w i t h salt. T h e a c t i v i t y
coefficients
are r e l a t e d t o t h e l i q u i d c o m p o s i t i o n b y u s i n g t h e two-constant W i l s o n
e q u a t i o n ( 3 ) except f o r systems w h i c h s h o w a r e g i o n o f i m m i s c i b i l i t y
w h e n t h e three-constant f o r m is necessary. O n e a d v a n t a g e o f t h e W i l s o n
e q u a t i o n o v e r other s e m i - e m p i r i c a l a p p r o x i m a t i o n s f o r i n t e g r a t i n g t h e
G i b b s - D u h e m e q u a t i o n is t h a t i t h a s a d e g r e e o f b u i l t - i n
dependence
form
f o r t h e l i q u i d - p h a s e a c t i v i t y coefficients.
temperature
T h e two-constant
gives:
m -
-W-AM-*))
in y, -
+ (i-x) { - ^
- H i - * ,
W h e n t h e best values o f A i a n d A
s i t i o n is c a l c u l a t e d :
2
ln(l-y)
= ((1-)' /) j(l-x)
X
j,^}
12
\ 1-A x
(2b)
have been found, the vapor
2 2
A
12
T^fb)} <*>
( -V )(II-p' )/RT -
xA
21
1-A
21
compo
ln(l-A x)
12
<>
3
(l-x)f
T h e t e r m i n v o l v i n g t h e m i x e d s e c o n d v i r i a l coefficients
was not used
because o f t h e u n c e r t a i n t i e s i n t h e values o f t h e s e c o n d v i r i a l
coefficients
of t h e p u r e c o m p o n e n t s .
Application
T h e m e t h o d d e s c r i b e d a b o v e is a p p l i e d t o t h e e t h a n o l - w a t e r
system
w h i c h has b e e n s a t u r a t e d i n t u r n w i t h e a c h of a w i d e r a n g e o f i n o r g a n i c
salts. T h e v a p o r pressure o f w a t e r s a t u r a t e d w i t h salts o v e r a t e m p e r a
t u r e range is a v a i l a b l e f o r m a n y salts (4).
F o r e t h a n o l these d a t a a r e
u n a v a i l a b l e , a n d a c o r r e c t i o n to t h e saturation v a p o r pressure is a p p l i e d
b y m u l t i p l y i n g b y t h e r a t i o o f t h e v a p o r pressure o f e t h a n o l s a t u r a t e d

11.
J A Q U E S
A N D
Prediction
F U R T E R
of Vapor
161
Composition
w i t h salt to the v a p o r pressure of p u r e e t h a n o l at the salt s o l u t i o n b o i l i n g

T h i s r a t i o , c,
point.
is a s s u m e d to
be
independent
of
temperature.
I n t e r p o l a t i n g l i t e r a t u r e d a t a y i e l d e d the r e q u i r e d v a l u e s of the
v o l u m e s of the t w o l i q u i d s ( 5 )
molar
at the a p p r o p r i a t e temperatures a n d the
s e c o n d v i r i a l coefficients of w a t e r ( )
and ethanol (7).
A n example
of
the fit is s h o w n i n T a b l e I.
Table I.
Calculated Vapor Compositions from Fit of Isobaric D a t a
EthanolWaterSaturated Ammonium Chloride (14)
X
.034
.074
.124
.170
.284
.446
.633
.759
.858
.938
G*/RT-x
fit
.495
.595
.646
.674
.696
.720
.752
.807
.869
.936
93.8
87.2
84.2
82.5
81.7
80.8
79.4
78.5
77.7
77.9
fit
(y-y)
(y-yc)
.000
-.012
-.007
-.005
-.001
-.003
-.019
-.012
-.006
.001
.003
-.007
.000
.004
.009
.005
-.016
-.014
-.011
-.003
.0098
.0098
Sample deviation
A s a n alternative, these d a t a w e r e also fitted to W i l s o n s free e n e r g y

equation:
(? /RT =
E
-x
ln(l-A (l-x))
21
(l-x)
(4)
ln{\-A x)
l2
a n d the v a p o r c o m p o s i t i o n w a s a g a i n c a l c u l a t e d b y u s i n g E q u a t i o n 3.
d i r e c t c o m p a r i s o n c a n b e m a d e b y e x a m i n i n g the s a m p l e d e v i a t i o n of
the v a p o r c o m p o s i t i o n f r o m b o t h
fittings.
T a b l e II presents the t w o sets
of s a m p l e d e v i a t i o n s b a s e d u p o n v a p o r c o m p o s i t i o n s .
a n d /
T h e values of
i n d i c a t e that some of the d a t a are of d u b i o u s a c c u r a c y i . e . ,
l o w consistency a n d / o r h i g h e x p e r i m e n t a l scatter.
of the o b s e r v e d -
G r a p h i c a l smoothing
d a t a w o u l d have r e d u c e d the values of the s a m p l e
deviations b y r e m o v i n g the e x p e r i m e n t a l scatter c o m p o n e n t , b u t i t w a s

c o n s i d e r e d d e s i r a b l e to use the r a w d a t a .
T h e v a l i d i t y of the -
e s t i m a t i o n for
the e t h a n o l - w a t e r
binary
w i t h o u t salt was c h e c k e d u s i n g three sets of l i t e r a t u r e d a t a . T h e results

are i n c l u d e d i n T a b l e II, a n d O t s u k i s d a t a ( S )
are s h o w n i n F i g u r e 1.
C a l c u l a t e d a n d e x p e r i m e n t a l y-values agree satisfactorily.

A d d i t i o n of a salt i n m a n y cases results i n a c o n s i d e r a b l y w i d e r b o i l i n g
range, a n d this w o u l d affect the heat of m i x i n g t e r m a n d l e a d to a p o o r e r
fit of the d a t a . H o w e v e r , this is u n l i k e l y to be a n i m p o r t a n t factor because

162
EXTRACTIVE
AND AZEOTROPIC
DISTILLATION
it has b e e n s h o w n ( 9 ) that a g o o d fit i s o b t a i n e d w i t h i s o b a r i c d a t a f o r

the m e t h a n o l - a n i s o l e system w h i c h has a 64 C b o i l i n g range.
Comparing
the t w o sets o f results i n T a b l e I I i n d i c a t e s that the G /KT-x
fit
i s gen
e r a l l y superior, b u t f o r t h e better d a t a as i n d i c a t e d b y s m a l l
sample
deviations o f pressure a n d free energy, t h e differences

c o n c l u s i o n is not u n e x p e c t e d .
In y = / ) -
However, if the following
(Bu-VOffl-p'O/RT
ttl-x)A
\ l-A x
l2
X )
are s m a l l .
12
This
equation
ln(l-A {l-x))
2l
xA
)
l-A (l-x)f
<>
5
21
21
is u s e d to c a l c u l a t e the v a p o r c o m p o s i t i o n i n s t e a d o f E q u a t i o n 3, i n every
case except f o r b a r i u m nitrate t h e opposite is true.
m a r g i n a l , a n d a n e x p l a n a t i o n is offered
Table II.
Salt
NH CI
4
tNaCl
t NaBr
t NaN0
tKCl
KBr
KI
K S0
Ca(N0 )
Ba(N0 )
CuCl
HgCl
HgBr
Hgl
LiCl"
t NaCl
t Na S0
tKCl
"
BaCl
KN0
(NH ) S(V
3
T h i s effect i s n o t
below.
Comparison of the T - * Fit and the G^/RT-x

the Wilson Equation
<sG RT
4.88
6.24
9.69
13.66
18.82
27.42
30.06
31.40
28.09
19.48
3.95
33.69
20.20
10.31
5.10
8.40
13.69
6.07
20.96
23.95
22.90
3.65
11.42
4.94
24.9
.0079
.0068
.0045
.0098
.0119
.0471
.0260
.0301
.0109
.0234
.0118
.0078
.0152
.0092
.0138
.0273
.0142
.0062
.0184
.0264
.0180
.0058
.0110
.0099
.0358
6.45
4.48
6.34
5.84
11.79
60.27
31.75
28.74
10.72
14.08
6.23
28.12
15.45
7.54
3.55
17.47
13.98
12.54
14.64
19.63
10.14
4.00
4.34
7.70
35.3
Fit Using
Reference
.0082
.0064
.0059
.0098
.0054
.0375
.0187
.0200
.0150
.0098
.0082
.0096
.0130
.0096
.0119
.0261
.0146
.0056
.0143
.0132
.0088
.0045
.0085
.0078
.0320
Data of limited range: x = 0.3-1.0.

Data of limited range: x = 0-0.8.
Data of limited range: x = 0.2-1.0.
Data of limited range: x = 0-0.6.
Partially miscible systems-use of three constant Wilson equation,
t See text.

8
12
18
U
14
15
u
U
15
15
U
11
u
u
16
17
18
17
16
U
19
14
11.
J A Q U E S
A N D
Prediction
F U R T E R
of Vapor
163
Composition
Figure 1. Comparison of the experimentally

de
termined vapor compositions for the
ethanol-water
system (8) with two constant Wilson T - x fit
Observed
Calculated
A n i n t e r e s t i n g a n o m a l y o c c u r r e d for the seven systems m a r k e d w i t h

a d a g g e r i n T a b l e II.
T h e o r i g i n a l c o m p u t e r p r o g r a m w h i c h was b a s e d
u p o n first o r d e r l i n e a r i z a t i o n of the n o r m a l e q u a t i o n s f a i l e d to find a

s o l u t i o n for the G V R T - x fit for these systems. A s e c o n d p r o g r a m u s e d
a more powerful
t e c h n i q u e w h i c h u s e d a n e w a p p r o a c h to
m e t r i c a l g o r i t h m s (10).
variable
B e c a u s e the t w o constants i n the W i l s o n e q u a
t i o n c a n n o t be greater t h a n u n i t y , a constraint is p l a c e d u p o n the p l a n e

w h e r e a s o l u t i o n is sought.
A i w a s r e p l a c e d b y 1-A
2
T o free the p r o g r a m f r o m this constraint,
and A
12
b y 1-B .
2
This program found a solu
t i o n , b u t it d i d n o t represent a true m i n i m u m . T h e s o l u t i o n o c c u r r e d at
a walli.e.,
where
A i =
1, a n d analysis s h o w e d that this w a s
lowest p o i n t of the A i - A i
2
the
p l a n e . A n a l y z i n g the r e m a i n i n g systems of
T a b l e II s h o w e d that a g e n u i n e m i n i m u m i . e . , a least v a l u e w h e r e the

first derivatives of the object f u n c t i o n v a n i s h w a s f o u n d i n a l l of these
cases.
T h e t w o systems c o n t a i n i n g p o t a s s i u m nitrate a n d a m m o n i u m s u l
fate e a c h h a v e a r e g i o n of p a r t i a l m i s c i b i l i t y . A d d i n g a t h i r d constant to
the W i l s o n e q u a t i o n allows c o r r e l a t i o n of s u c h systems. T h e results are
s h o w n i n T a b l e II a n d F i g u r e 2. ( T h e b r o k e n l i n e of F i g u r e 2 is a feature
of systems w h i c h s h o w m a t e r i a l i n s t a b i l i t y . A g r a p h of m o l a r free energy

164
E X T R A C T I V E
A N D
A Z E O T R O P I C
DISTILLATION
of m i x i n g as a f u n c t i o n of l i q u i d m o l e f r a c t i o n shows a c o n v e x u p w a r d s
p o r t i o n w h e r e a r e g i o n o f p a r t i a l m i s c i b i l i t y exists (20).
The
vapor-
l i q u i d e q u i l i b r i u m c u r v e s h o u l d , of course, b e h o r i z o n t a l i n the r e g i o n of
t w o l i q u i d phases, b u t the f o r m of the e q u a t i o n m u s t g i v e a c o n t i n u o u s
c u r v e a n d h e n c e c a n n o t p r e d i c t a h o r i z o n t a l l i n e , w h i c h w o u l d a m o u n t to
a r e g i o n of d i s c o n t i n u i t y i n the e q u a t i o n . )
T h e t w o - c o n s t a n t W i l s o n e q u a t i o n w a s c h o s e n as t h e c o r r e l a t i n g
e q u a t i o n r a t h e r t h a n t h e three-constant R e d l i c h - K i s t e r e q u a t i o n (21)
for
t w o reasons. I n a m a j o r i t y of the systems the s a m p l e d e v i a t i o n of v a p o r

c o m p o s i t i o n w a s smaller, a n d i n c e r t a i n cases the R e d l i c h - K i s t e r e q u a t i o n
e r r o n e o u s l y p r e d i c t e d phase s e p a r a t i o n . F i g u r e 3 shows s u c h a n e x a m p l e .
T a b l e I I I gives a c o m p l e t e l i s t i n g of m , c, c, A21,
A , a n d C values
i 2
w h i c h a l l o w us to estimate the v a p o r c o m p o s i t i o n s of e t h a n o l - w a t e r m i x
tures c o n t a i n i n g a w i d e r a n g e of i n o r g a n i c salts.
Discussion
D i f f e r e n t object functions ( , y, In 72/71, etc. ) h a v e b e e n u s e d for
m a n y years; w h e n d i s c r e p a n c i e s h a v e a r i s e n , at least one a u t h o r
2 LAYERS H
.1
.2
.3
.4
.5
X
.6
.7
.8
.9
Figure 2. Comparison
of the experimentally
de
termined vapor compositions for the
ethanol-watersaturated potassium nitrate system (19) with the
three constant Wilson T - x fit
Observed
Calculated

(22)
11.
J A Q U E S
A N D
Prediction
F U R T E R
.1
.2
.3
.4
of Vapor
.5
X
.6
.7
Composition
.8
165
.9
Figure 3. Comparison
of experimentally
deter
mined vapor compositions for the
ethanol-watersaturated potassium sulfate system (14) with (a)
two constant Wilson T-x fit and (b) three constant
Redlich-Kister
T-x fit
Observed
Calculated
(a)
(b)
has a t t r i b u t e d t h e m to errors i n d a t a . A c t u a l l y , there are three possible

sources of e r r o r :
1. T h e W i l s o n e q u a t i o n is a n i m p e r f e c t m o d e l . I n t h e i s o b a r i c case
the effect of n e g l e c t i n g the t e m p e r a t u r e d e p e n d e n c e of A i a n d A
and
i n u s i n g the G i b b s D u h e m e q u a t i o n , w h i c h w a s d e r i v e d for constant
t e m p e r a t u r e a n d pressure, a d d to the i n h e r e n t i m p e r f e c t i o n .
2
12
2. A l l the e x p e r i m e n t a l d a t a are subject to error, a n d i n t h e salt

effect field a n a d e q u a t e e s t i m a t i o n of e x p e r i m e n t a l errors is r a r e l y m a d e .
F o r e x a m p l e , w i t h o u t d o i n g a statistical treatment of the error i n the
m e a s u r i n g of t e m p e r a t u r e , a s i m p l e e s t i m a t i o n of r a n d o m e x p e r i m e n t a l
error b a s e d u p o n the g r a p h i c a l s m o o t h i n g of b o i l i n g p o i n t - c o m p o s i t i o n
d a t a for eight systems c o n t a i n i n g w a t e r , m e t h a n o l o r e t h a n o l , a n d a n
acetate salt at s a t u r a t i o n [ t a k e n f r o m the literature ( 2 3 ) ] suggested a n
o v e r a l l average error of 0 . 9 C o n the b o i l i n g p o i n t s .
3. T h e w h o l e p r o c e d u r e , w i t h o r w i t h o u t salts, m a y n o t b e b a s e d
u p o n s o u n d statistical p r i n c i p l e s . R a t h e r t h a n u s i n g v a r i o u s object f u n c
tions, i t appears better t o use a r e l i a b l e statistical t e c h n i q u e s u c h as t h e
m e t h o d of m a x i m u m l i k e l i h o o d (24)
o r the B a y e s i a n a p p r o a c h
(25),
b o t h of w h i c h take i n t o a c c o u n t the errors i n a l l e x p e r i m e n t a l o b s e r v a
tions i n a l o g i c a l l y justifiable f a s h i o n . T h e v a r i o u s d i s c r e p a n c i e s a n d
anomalies n o t e d i n the present w o r k w o u l d b e m o d e r a t e d b y u s i n g either

166
EXTRACTIVE
Table III.
const.
'
.9294
.9935
.9174
.8853
.9547
.9572
.9383
.9962
1.0712
1
1
1
1
1
.9659
.9935
1.019
.9640
BaCl
KN0
(NH ) S0
3
AZEOTROPIC
DISTILLATION
Constants for the Fit Using the Wilson Equation
Salt
NH4CI
NaCl
NaBr
NaN0
KC1
KBr
KI
K S0
Ca(NO,)
Ba(N0 )
CuCl
HgCl
HgBr
Hgl
LiCl
NaCl
Na S0
KC1
KI
AND
A M
.8140
.7899
.8526
.8829
.9476
.9138
.9420
.9198
.9214
.8433
.9188
.8531
.8208
.8486
.8314
.8428
.8267
.7926
.9332
.9349
.9307
.1325
.1813
.0848
.4154
.3692
.5005
.5592
.4314
.2744
.4000
.0802
.0090
.1780
.0565
.0791
.1263
.1095
.5457
.3308
.1633
.3226
.3285
.2142
-.0032
.1109
.0776
-.0704
-.0037
.0360
.0719
.0105
.9368
0
0
0
0
0
.9199
.1109
.0969
.0235
1.013
1.019
0.912
1.020
1.000
0.983
0.886
1.023
0.747
1.027
1.042
.892
.965
1.010
.492
1.019
1.000
1.000
.9383
.0719
.9275
.9906
.8570
.0348
.975
1
-.2250
.0487
1.000
1.011
.7515
.9409
.9731
.9170
Refere
8
12
13
14
15
14
14
15
15
11
11
14
14
14
14
16
17
18
17
16
11
- . 3 9 0 8 2.959
.0449 1.250
19
14
estimate w i t h the o n l y sources of error b e i n g i n the observations a n d i n

the p h e n o m e n o l o g i c a l m o d e l .
Conclusions
A
method
has b e e n
d e v e l o p e d for c a l c u l a t i n g e q u i l i b r i u m
vapor
c o m p o s i t i o n s , b a s e d o n b o i l i n g p o i n t vs. l i q u i d c o m p o s i t i o n d a t a ,
for
systems saturated w i t h a salt. S u c h ternary systems i n effect h a v e b e e n

treated as b i n a r i e s (26)
i n w h i c h the s t a n d a r d state of e a c h of t h e t w o
l i q u i d c o m p o n e n t s is that of b e i n g saturated w i t h salt i n s t e a d of b e i n g p u r e

and w i t h the pure-component
example,
v a p o r pressures b e i n g so adjusted.
i n the e t h a n o l - w a t e r - s a l t
t e r n a r y systems
b e e n c o n s i d e r e d as b i n a r i e s c o m p o s e d
tested, t h e y
For
have
of w a t e r s a t u r a t e d w i t h salt as
one c o m p o n e n t a n d e t h a n o l saturated w i t h salt as t h e other
component.
I n the testing to w h i c h i t has b e e n subjected so far, the m e t h o d seems

encouraging.

11.
J A Q U E S
A N D F U R T E R
Prediction
of Vapor
Composition
167
Acknowledgment
T h e r e s e a r c h f o r this p a p e r w a s s u p p o r t e d b y t h e D e f e n c e R e s e a r c h
B o a r d o f C a n a d a , G r a n t n u m b e r 9530-40. T h e authors are g r a t e f u l t o
F . M . L a r k i n o f t h e C o m p u t e r C e n t r e at Queen's U n i v e r s i t y , K i n g s t o n ,
for m a n y h e l p f u l discussions.
Lest of
Symbols
Subscripts:
1 = ethanol
2 = water
c = calculated value
A21, A12, C = e m p i r i c a l constants i n W i l s o n e q u a t i o n
A,B
= e m p i r i c a l constants f o r use w i t h F l e t c h e r s s u b r o u t i n e
Bu
= s e c o n d v i r i a l coefficient o f c o m p o n e n t i
G
= excess free e n e r g y o f m i x i n g
In
= natural logarithm
log
= l o g a r i t h m t o the base 10
m, const.
= e m p i r i c a l constants i n the e q u a t i o n :
l o g p'2 = l o g p 2 const,
p'i
= v a p o r pressure o f c o m p o n e n t i s a t u r a t e d w i t h salt
R
= gas constant
= absolute t e m p e r a t u r e
Vi
= molar volume of component i
x
= m o l e f r a c t i o n o f e t h a n o l i n the l i q u i d phase, c a l c u l a t e d o n
a salt-free basis
y
= mole fraction of ethanol i n the vapor phase
7i
= a c t i v i t y coefficient o f c o m p o n e n t i
e
= r a t i o o f v a p o r pressure o f e t h a n o l s a t u r a t e d w i t h salt to
t h e v a p o r pressure o f p u r e e t h a n o l at t h e salt s o l u t i o n
boiling point
= t o t a l pressure
/
= s a m p l e d e v i a t i o n o f t h e excess free e n e r g y i n E q u a t i o n 4
= s a m p l e d e v i a t i o n o f the v a p o r c o m p o s i t i o n c o r r e s p o n d i n g
to E q u a t i o n 4
= s a m p l e d e v i a t i o n o f the t o t a l p r e s s u r e i n E q u a t i o n 1
= s a m p l e d e v i a t i o n o f the v a p o r c o m p o s i t i o n c o r r e s p o n d i n g
to E q u a t i o n 1
E
Literature Cited
1. MacKay, D., Salvador, R. T., Ind. Eng. Chem. Fundamentals (1971) 10,
167.
2. Barker, J. ., Australian J. Chem. (1953) 6, 207.
4. International Critical Tables, pp. 362-374, Vol. III, McGraw-Hill, New
York, 1929.
5. Prausnitz, J. M., Eckert, C. ., Orye, R. V., O'Connell, J. P., "Computer
Calculations for Multicomponent Vapor-Liquid Equilibrium," Appendix
B, Prentice-Hall, 1967.

168
EXTRACTIVE AND AZEOTROPIC DISTILLATION
6. Rowlinson, J. S., Trans. Faraday Soc. (1949) 45, 974.

7. Lambert, J. D., Discussions Faraday Soc. (1953) 15, 226.
8. Otsuki, H., Williams, F.C.,Chem. Eng. Progr. Symp. Ser. 6 (1953) 49, 55.
9. Cukor, P. M., Prausnitz, J. M., Intern. Symp. Distillation, Inst. Chem. Eng
(London), Section 3B, p. 73 (1969).
10. Fletcher, R., U.K. At. Energy Authority Kept. TP383 (1969).
11. Rius Mir, ., Alvarez Gonzalez, J. R., Uriante Hulda, ., Anales Real. Soc.
Espan. Fis. Quim. (Madrid) (1960) 56B, 629.
13. Furter, W. F., Ph.D. Thesis, University of Toronto, 1958.
14. Johnson, A. I., Furter, W. F., Can. J. Chem. Eng. (1960) 38, 78.
15. Meranda, D., Furter, W. F., A.I.Ch.E. Journal (1972) 17, 38.
16. Rius Mir, ., Otero de la Gandara, J. L., Alvarez Gonzalez, J. R., Anales
Real. Soc. Espan. Fis. Quim. (Madrid) (1957) 53B, 185.
17. idem., ibid. (1957 53B, 171.
18. Tursi, R. R., Thompson, A. R., Chem. Eng. Progr. (1951) 47, 304.
20. Rowlinson, J. S., "Liquids and Liquid Mixtures," p. 144, 2nd ed., Butterworth, 1969.
21. Redlich, O., Kister, A. T., Ind. Eng. Chem. (1948) 40, 345.
22. Newton, ., Intern. Symp. Distillation, Inst. Chem. Engrs. (London), Section 3B, p. 82 (1969).
23. Meranda, D., Furter, W. F., A.I.Ch.E. J. (1971) 17, 38.
24. Kendall, M. G., Stuart, ., "The Advanced Theory of Statistics," Vol. II,
2nd ed., Griffin, London, 1967.
25. Lindley, D. V., "Introduction to Probability and Statistics from a Bayesian
Viewpoint," Cambridge, 1965.
26. Jaques, D., Furter, W. F., A.I.Ch.E. J. (1972) 18, 343.
RECEIVED January 11, 1972.

INDEX
A
Acetone
43
azeotrope, methanol
47
-methanol separation
48
system acetic a c i d 136
Acid, Lewis
50
Activity coefficients
17,124,140
dilution
49
liquid phase
2,3,150,151
paraffin
20
selectivity and
27
ADP
-ADPLLE
91
simplified calculations by
subprogram
68
A D P P L L E , subprogram
69
Agent, separating
37
Air pollution
148
Alcohols, mixtures of water and
simple
93
Algorithm, modification of
correction
131
Alternate solvent recovery
32
Analysis
economic
24
regression
155
venture
24
Applications
43
Aqueous
ethanol
calculated azeotropic distilla
tion results compared for
dehydrating
65
dehydrating
14
mixtures, dehydration of . . . .
2
systems
41
Aromatics
58
Association
complexes
17, 42
factors, vapor, and liquid
138
Automated feature, use of the . . . .
69
Azeotrope
38,110
methanol-acetone
47
of water and entrainers
112
Azeotropic
column
115
distillation
14,65
batch
115
column
12
comparison of extractive with
12
modified
115
Azeotropic (Continued)
distillation
ternary
wo,
ADP/ADPLLE
results compared for dehydrat
ing aqueous ethanol,
calculated
or extractive distillation
columns
*
65
65
93
Barker's method
159
Base, Lewis
*
50
Basic
flow
114
Basis
cost calculation
25
design
23
Batch azeotropic distillation
115
Benzene
65, 89
and diethyl ether, comparison
for the entrainers, n-pentane
87
Binary system
99
Boiling point
107
Bonding solvents, hydrogen
21
Bottom product
12
1,3-Butadiene recovery
33
Butanol
HI
C
Calcium chloride
Calculated azeotropic distillation
results compared for dehydrat
ing aqueous ethanol
Calculation
basis, cost
computer
design
distillation
for the extractive distillation of
aqueous ethanol mixtures . .
sequence
by subprogram A D P , simplified .
tray-to-tray
Changing the molecular environ
ment
Chemistry of the salt effect
Choice of an entraner
C3 hydrocarbon mixtures
C4 hydrocarbon separations
171

39
65
25
64
91
122
4
125
68
70
1
40
87
34
33
172
E X T R A C T I V E
Circulation rate
17
solvent
24
Clay, colloidal
120
Coefficient
activity
17,124,140
dilution activity
49
distribution
64
fugacity
97
imperfection-pressure
2
liquid phase activity
3,150,151
paraffin activity
20
selectivity and activity
27
Cohesive
density, polar
51
energy, polar
48
Coke
119,120
Colloidal clay
120
Column
35
azeotropic
115
distillation
12
or extractive distillation
93
efficiency
24
extractive distillation
6
profiles
84
solvent recovery
10,11
Comparison
for the entrainers, n-pentane,
benzene, and diethyl ether
87
of extractive with azeotropic
distillation
12
Complexes, association
17, 42
Components, feed
1,17, 22, 40
Composition
7, 35, 94,125,146
liquid
107
vapor
41,159
phase
97
Computer
calculations
64
methods, multicomponent
157
Concentration
molal salt
40
saturation
39
solvent
19
Condenser temperature
131
Consistency test
146
Content, water
110,114
Cooler, solvent
17
Correction
algorithm, modification of
131
matrix, Jacobian
126
Cost
calculation, basis
25
30
utility
26
Cracking
119
Criteria, solvent selection
18
D
Dalton's law
152
Data, isobaric vapor-liquid
equilibrium
96,124,136
Debye, electrostatic theory of . . . .
42
Dcantation
114
A N D
A Z E O T R O P I C
DISTILLATION
Dehydrating
aqueous ethanol
14
calculated azeotropic distillation results
65
process, demulsifying
114
Dehydration of aqueous ethanol
mixtures
1,118
Demulsification of crude oils
108
Demulsifying, dehydrating process
114
Density, polar cohesive
51
Design
basis
16,23
calculations
91
process
16,106
of separation processes
2
Diethyl ether
65,89
comparison for the entrainers,
n-penane, benzene, and
diethyl ether
87
Digital computers
2
Dilution
activity coefficients
48
relative volatilities through
G L C , infinite
59
Dipole-induced dipole
49
Dispersion
49
Dissolution, feed
117
Dissolved salt
37
Distillation
of aqueous ethanol mixtures,
calculations for the
4
azeotropic
14, 65
batch azeotropic
115
calculations
122
column
azeotropic
12,13, 93
extractive
6,13,93
continuous
115
costs, extractive
30
extractive
1,12,14,16,148
modified azeotropic
115
program
A D P / A D P L L E , azeotropic . .
65
ternary azeotropic
68, 72
results compared for dehydrating aqueous ethanol, calculated azeotropic
65
solvents
ethylene glycol as the extractive
2
extractive
58
screening of extractive
46
using dissolved salts as separating
agents, extractive
40
Distribution coefficients
64
Ease of separation
Effect
chemistry of the salt
magnitude of salt
mixed solvents

40, 46
35, 40
41
52
173
INDEX
Effect (Continued)
of solvent and solute concentration
50
Efficiency, column
24
Electrolytes, solution theory of . . .
40
Electrostatic theory of Debye . . . .
42
Energy, Gibbs free
95
Energy
molar free
163
polar cohesive
49
Enthalpies for liquid and vapor . . 4,124
Entraner
12,64,65,110
azeotropes of water and
112
choice of
87
n-pentane, benzene, and diethyl
ether, comparison for the . .
87
solvent
116
Entrainment
37
Environment, changing the
molecular
1
Equation
Gibbs-Duhem
155
modified van Laar
3, 66
non-random, two liquid
93
nonlinear
122
NRTL
Redlich-Kister
164
van Laar
132
vapor pressure
3
Wilson
95,160
Equilibria
data
124
isobaric vapor-liquid
93,136
prediction of three-phase
65, 66
relative volatilities for three
phase
67
relation, modified
139
salt effect on vapor-liquid
40
separation system
123
stage requirements
28
three-phase
67
vapor-liquid
35, 67,148
Ethanol
13,39, 86, 89,93
calculated azeotropic distillation
results compared for dehydrating aqueous
65
calculations for the extractive
distillation of aqueous
4
mixtures
dehydration of aqueous
1,2
recovery of
7
-water
38,41,97,160
Ethylene glycol
1, 2,12
-water
41
Extraction, primary
119
Extractive distillation
1,12,14,16,132,148
of aqueous ethanol mixtures,
calculations for the
4
columns, azeotropic or
6, 93
costs
30
solvent
58
ethylene glycol as the
2
Extractive distillation (Continued)

solvent
screening of
using dissolved salts as separating
agents
46
40
F
Factor, separation
17, 59
Factors, vapor and liquid associations
138
Feed
5
components
17, 22, 40
dissolution
117
Feedstock
113
Flow
basic
114
vapor
129
Flowsheet
18,111,157
Foaming
114
Fraction, naphtha
Ill
Fractionation, reverse
28
Free energy
95,161
molar
163
Fugacity coefficients
94,97
G
G C O S process
118
Gibbs-Duhem equation . . . 146,155,159
Gibbs energy
42,95
GLC
infinite dilution relative volatilities through
59
screening solvents through . . . .
58
Great Canadian Oil Sands, Ltd.
( G C O S ) Process
118
H
Heat
loads
14
recovery system
30
Hydration
43
Hydrocarbon
55,93,109
C
4
mixtures
48
separations, C4
33
Hydrogen bonding solvents
21
Hypothetical saturation vapor
pressure
138
3
I
Imperfection-pressure coefficients .
2
Infinite dilution relative volatilities
through G L C
59
Internal pressure
42
Isobaric vapor-liquid
equilibrium data
93,136
systems
159
Isothermal-isobaric system
155
Iteration variables
125,127

174
E X T R A C T I V E
J
Jacobian correction matrix
126,128
values
Kerosene
Knockback section, solvent
9
117
37, 44
L
Law, Raoult's
18,101
Layer, top bitumen
121
Lewis
acid
50
base
50
and Matheson technique
70
Limit, miscibility
22
Liquid
associations factors, vapor and . 138
composition
107
equation, non-random, two . . . .
93
equilibrium data, isobaric
vapor35,93,136,148
-liquid tieline
153
phase
activity coefficients . . . 2,3,150,151
miscibility
107
systems, isobaric vapor159
and vapor, enthalpies for
4
phases, relative distributions
between the separable . .
2
Loading, solvent
24
Lowest water content
89
M
Matrix, Jacobian correction . . . . 122,126
Matheson technique, Lewis and . .
70
Mercuric chloride
41
Methanol
-acetone azeotrope
47
separation, acetone48
Method
Marquardt's
134
non-hydrocarbon mixtures: The
Schiebel
47
Parachor
56
Weimer-Prausnitz ( W P )
57
multicomponent computer
157
Newton
134
3-Methyl-l-butanol-water
100
Methyl ethyl ketone, water148
Miscibility
limit
22
liquid-phase
107
Mixed solvents effect
52
Mixture
THF-MEK
149
C3 hydrocarbon
34, 48
nonideal
122
ternary
96
of water and simple alcohols . . .
93
A N D
A Z E O T R O P I C
DISTILLATION
Mixture (Continued)
the Scheibel Method, nonhydrocarbon
47
Modification
of correction algorithm
131
process
29
Modified
azeotropic distillation
115
equilibrium relation
139
Redlich-Kister test
140
van Laar equations
3, 66
Molal salt concentration
40
Molar free energy
163
Molecular environment, changing
the
1
Multicomponent systems
13,17,157
Naptha fraction
HI
Newton's methods
122,134
Non-hydrocarbon mixtures: the
Scheibel Method
47
Nonideal mixtures
122
Nonideality
1,95
Nonlinear equations
122
Non-random, two-liquid equation .
93
Notation, matrix
122
N R T L equation
96
Octane
Oil
wet sludge
demulsification of crude
Olefins
Operating temperature
Optimum design
Othmer recirculation still
HI
115
108
58
24
16
43
Parachor method
56
Paraffin
activity coefficient
20
-olefin system
19
n-Pentane
1,12,65,89
benzene and diethyl ether,
comparison for the entrainers
87
Petroleum crudes
108
P P,
47
Polar
cohesive
density
51
energy
49
solvent
20
Pollution, air
148
Potassium acetate
37
Prediction of three-phase equilibria
66
Pressure
94,107
coefficients, imperfection2
equations, vapor
3
t

175
INDEX
Pressure (Continued)
hypothetical saturation vapor . .
138
vapor
110
Process
demulsifying, dehydrating
114
design
16,106
Great Canadian Oil Sands, Ltd.
( G C O S ) process
118
of separation
2
modifications
29
Product, top
5,12, 86
A D P / A D P L L E , azeotropic
distillation
65
ternary azeotropic distillation... 68, 72
Propane
33
separation of propylene
16
Propylene
33
propane, separation of
16
R
Raoult's Law
18,101,152
Rate
circulation
17
solvent circulation
24
Reboiler temperature
131
Recirculation still, Othmer
43
Recovery
alternate solvent
32
1,3-butadiene
33
column, solvent
10,11
ethanol
7
and recycle step
37
system, heat
30
Recycle step, recovery and
38
Redlich-Kister
equation
164
test, modified
140
Regression analysis
155
Relation, modified equilibrium . . .
139
Relationship, Gibbs-Duhem
146
Requirements, equilibrium stage . .
28
Reverse fractionation
28
Runs, two-phase
153
S
Salt
35,159
concentration, molal
40
dissolved
37
effect
35
chemistry of the
40
magnitude of
41
on vapor-liquid equilibrium .
40
free
39
molecules, undissociated
41
as separating agents, extractive
distillation using dissolved .
40
Saturation
159
concentration
39
vapor pressure, hypothetical . . .
138
Scheibel method, non-hydrocarbon
mixtures: the
47
Screening
of extractive distillation solvents
46
solvents through G L C
58
Section, solvent knockback
37
Selection criteria, solvent
18
Selectivity
18,47
and activity coefficients
27
Separating agent
37
C4 hydrocarbon
33
extractive distillation using dissolved salts as
40
Separation
91
acetone-methanol
48
ease of
40, 46
factor
17,59
of propylene-propane
16
solvent
156
system, equilibrium
122
Silt
108
Simplified calculations by subprogram A D P
68
Sludge, oil-wet
115
Solubility
113
Solute concentration, effect of
solvent and
50
Solution theory of electrolytes . . . .
40
Solutions, ideal
47
Solvent
35,47,114
circulation rate
24
concentration
19
cooler
17
effect, mixed
52
ethylene glycol as the extractive
distillation
2
evaluating
19
58
through G L C , screening
58
hydrogen bonding
21
knockback section
37
loading
24
polar
20
Solvent recovery column
10,11,32
screening of extractive distillation
46
Selection criteria
18
separation
156
and solute concentration, effect
of
50
volatility
22
Stage requirements, equilibrium . .
28
Step, recovery, and recycle
38
Still, Othmer recirculation
43
Stripping trays
11
Submatrices, Jacobian
128
Subprogram
A D P , simplified calculations by .
68
ADPPLE
69
System
acetic acid-acetone
136
aqueous
41
binary
99
equilibrium separation
122
ethanol-water
97,160

176
E X T R A C T I V E
System (Continued)
isobaric vapor-liquid
multicomponent
paraffin-olefin
ternary
159
17,93
19
103
Temperature . . . .7, 54, 94,110,125,161

denser
131
operating
24
reboiler
131
Ternary
azeotropic distillation program .
69
mixtures
96
separation by distillation
156
system
103
Test
consistency
146
modified Redlich Kister
140
Tetrahydrofuran
148
Theory
of Debye, electrostatic
42
of electrolytes, solution
40
T H F - M E K mixture
149
Three-phase equilibria
66
relative volatilities for
67
Top bitumen layer
120
Top product
5,12, 86
Transport
119
Tray-to-tray
70,71
Trays, stripping
11
Two
liquid equation, non-random . . .
93
phase runs
153
U
Undissociated salt molecules
U N I V A C 1108 computer
Use of the automated feature
41
4
69
A N D
AZEOTROPIC
DISTILLATION
Utility costs
phase
composition
26
2
97
van der Waal forces

42
van Laar equation
95,132
Vapor
composition
41,159
enthalpies for liquid and
4
flows
129
relative distributions between
the separable liquid and
2
-liquid equilibria
35,67,148
and liquid associations factors . .
138
pressure
110
equations
3
hypothetical saturation
138
Variable, iteration
127
Vector differentiation
126
Venture analysis
24
Viscosity
108
V L E data
96
Volatilities
17, 40,47, 89,104,145
through G L C , infinite dilution
relative
59
profiles
7
solvent
22
W
Water
content
11,110,114
lowest
89
and entrainers, azeotropes
112
ethanol38,41,160
ethylene glycol41
methyl ethyl ketone
148
and simple alcohols, mixtures of
93
Weimer-Prausnitz ( W P ) method .
56
Wilson equation
95,160


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Extractive and Azeotropic

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