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
ADVANCES IN CHEMISTRY SERIES 115
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 I N C H E M I S T R Y SERIES w a s f o u n d e d i n 1 9 4 9 b y the
A m e r i c a n C h e m i c a l S o c i e t y as a n outlet for s y m p o s i a a n d c o l -
lections of d a t a i n s p e c i a l areas o f t o p i c a l interest that c o u l d
n o t b e a c c o m m o d a t e d i n the Society's journals. It provides a
m e d i u m for symposia that w o u l d otherwise be fragmented,
t h e i r p a p e r s d i s t r i b u t e d a m o n g s e v e r a l journals o r not p u b -
l i s h e d at a l l . P a p e r s are refereed c r i t i c a l l y a c c o r d i n g t o A C S
e d i t o r i a l standards a n d r e c e i v e the c a r e f u l a t t e n t i o n a n d p r o c -
essing c h a r a c t e r i s t i c of A C S p u b l i c a t i o n s . Papers p u b l i s h e d
in A D V A N C E S I N C H E M I S T R Y SERIES are o r i g i n a l c o n t r i b u t i o n s
not p u b l i s h e d elsewhere i n w h o l e o r major p a r t a n d i n c l u d e
reports o f research as w e l l as r e v i e w s since s y m p o s i a m a y e m -
b r a c e b o t h types of presentation.

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 Propylene-

Propane
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
DIMITRIOS P. TASSIOS 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) to
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) 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 tray-
to-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 distil-
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) a n d the
e m p i r i c a l correlations o f P i e r o t t i et ah (7), 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 . A l s o use o f salts as
e x t r a c t i v e agents (12) 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-to-
t 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), and
the l o c a l effective m o l e fractions ( L E M F ) e q u a t i o n (15, 16), a two-
parameter v e r s i o n o f the b a s i c a l l y three-parameter NRTL equation.
L a r s o n a n d Tassios (17) 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 are
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) 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 (24),
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 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 greatly
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 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.
DIMITRIOS P. TASSIOS
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.

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 eth-
anol from water. Methods published earlier by one of the
authors are applied to calculate phase equilibria in a com-
puter calculation of the separation. The extractive distilla-
tion results are tabulated, represented graphically, and
discussed to illustrate extractive distillation as a method for
dehydrating aqueous ethanol mixtures. The results are com-
pared with corresponding results obtained by azeotropic
distillation with n-pentane as entrainer. They show extrac-
tive 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 -

2 E X T R A C T I V E A N D A Z E O T R O P I C DISTILLATION
Table I. Constants for Calculating Imperfection-Pressure Coefficients
P ,Atm.
c E' m X
Ethanol 516.3 63.1 0.089 4.75 75.9

Ethylene glycol 761.11 84.04 0.089 4.75 79.2
Water 647.00 218.0 0.026 4.75 24.7

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, m
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 three

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. 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 . A
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 DITSLER Dehydration of Ethanol Mixtures 3
Table II. Constants for Vapor Pressure Equations 0
A B C
Ethanol 8.16280 1623.22 228.98

Ethylene glycol 7.71147 1816.34 178.603
Water 20.844* 2817.4* 4.04859*
a
Antoine equations.
5
Log = A - BIT - 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 ) h a v e b e e n u s e d to c a l c u l a t e
t h e l i q u i d phase a c t i v i t y coefficients. Coefficients at three temperatures
are g i v e n i n T a b l e III. 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 IV
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 . 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
H^^îU), (2)
w h e r e t h e differential heat of m i x i n g (Li) x is g i v e n as
(L). = 2.303#( l o g < ) . / ( 1 / ) (3)
Table III. Modified van Laar Coefficients for the System

Ethanol-Ethylene G l y c o l - W a t e r
Binary % Ai, A c t,C
Ethanol-ethylene glycol 0.276000 0.259279 0.000000 75.0

Ethanol-water 0.728000 0.407000 0.000000 75.0
Ethylene gly col-water 0.001680 0.001000 0.000000 75.0
Ethanol-water 0.74600 0.40080 0.000000 87.8
E t h y l e n e glycolwater 0.00142 0.00081 0.000000 87.8
Ethanol-water 0.76050 0.39250 0.000000 100.0
Ethylene glycol-water 0.00130 0.000714 0.000000 100.0

Table IV. Enthalpies for Liquid and Vapor
h (liquid) H ( vapor)
t F Btu/lb. mole Btu/lb. mole
Ethanol 32 0.00 19800.0

100 2506.1 20937.9
200 6034.9 22573.3
300 10365.3 23969.2
Ethylene glycol 100 3637.0 30724.0

200 7535.0 32828.0
300 11600.0 35193.0
400 15889.0 37700.0
Water 100 1225.0 19916.0
200 3027.0 20649.0
300 4820.0 21290.0
Distillation 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%
-
200
I S/F = 2.5 (MOLE)
150

< y 75%

LU
100 h-
eg
LU ^^77.78%
50
- i
80%
: 1 r , 1
.0 1.8 2.6 3.4
R/F (MOLE BASIS)
Figure I . Effects on product purity of changing solvent-feed and reflux-
feea ratios
99% recovery of ethanol in the extractive distilfotion with ethylene glycol at
14.7 psia

2 3 4 5
ETHYLENE GLYCOL/ANOL (MOLE BASIS)
Figure 2. Effect of solvent-feed ratio on product purity in the extractive
distillation of aqueous ethanol with ethylene glycol
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. A t low solvent-feed ratios t h e m i n i m u m i s m o r e
pronounced. A t high solvent-feed 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

24
REBOILER
20
16
CONDENSER
12
2 8
1
3 4
ETHYLENE GLYCOL/ETHANOL RATIO, MOLES
Figure 3. Reboiler and condenser heat loads vs. solvent-feed ratio
99% 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 top
Table V . Extractive Distillation Column

Ethanol-Ethylene G l y c o l - W a t e r at 14.7 Psia e
Material Balance b
Top Bottom
Product Product
Components Feed/Moles Solvent/Moles Moles Moles
Ethanol 0.8564 0.856315 0.000085

Ethylene glycol 0.0000 3.5000 0.000001 3.499999
Water 0.1436 0.000014 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.

Table VI. Extractive Distillation Column

Temperature, Composition, and Volatility Profiles
Ethanol in Water in
Vapor, Mole Liquid, Mole a
Tray No. t, F Fraction Fraction psia W/E
Condenser 104.0 0.999983 0.000016 8.20

46 156.9 0.999984 0.000015 10.20 1.11
44 158.7 0.999793 0.000013 10.4 1.09
43 195.3 0.987189 0.000011 10.5 0.485
42 195.8 0.987120 0.000019 10.6 0.486
40 196.6 0.98696 0.00005 10.8 0.488
38 197.5 0.98677 0.00011 11.0 0.489
36 198.4 0.98648 0.00024 11.2 0.490
34 199.2 0.98601 0.00051 11.4 0.492
32 200.0 0.98517 0.00107 11.6 0.493
30 200.9 0.98356 0.00220 11.8 0.493
28 201.7 0.98037 0.00454 12.0 0.492
26 202.7 0.97395 0.00934 12.2 0.489
24 203.7 0.96087 0.01926 12.4 0.482
22 194.8 0.93873 0.04539 12.6 0.532
20 195.5 0.93854 0.04546 12.8 0.533
18 196.3 0.93827 0.04561 13.0 0.534
16 197.0 0.93772 0.04600 13.2 0.535
14 197.7 0.93615 0.04731 13.4 0.535
12 198.5 0.93079 0.05201 13.6 0.532
10 199.5 0.91132 0.06951 13.8 0.516
8 202.0 0.83701 0.13805 14.0 0.452
6 218.5 0.53735 0.35352 14.2 0.274
4 246.2 0.07283 0.46407 14.4 0.208
2 297.9 0.00349 0.19499 14.6 0.311
1 362.1 0.00054 0.03941 14.6 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 solvent-feed
r a t i o is 3.5 m o l e basis. 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 are
summarized in Table VI.

Figure 4. Temperature profile in extractive distillation of aqueous ethanol

99.99% recovery of ethanol, ethylene glycol/ethanol ratio = 4.08688 moles, reflux-
feed 1.5537 moles
NUMBER OF TRAYS (EQUIL.)

Figure 5. Volatility profiles in the extractive distillation of aqueous
ethanol with ethylene glycol
EG/ = 4.08688, R/F = 1.5537 moles, 99.99% recovery, ethanol

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 6. Composition profiles in the extractive distillation of
aqueous ethanol with ethylene glycol
EG/ = 4.08688 moles, R/F = 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

91 %m. 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 and Composition Profiles
Water in Ethylene Glycol

Vapor, Mole in Liquid, a
Tray No. t, F Fraction Mole Fraction psia EG/W
10 C o n d . 104.0 0.99936 .00004 12.28

9 Top 209.5 0.99936 .00176 13.98 .0216
8 213.3 0.99830 .06686 14.07 .0224
7 264.6 0.93928 .64743 14.16 .0352
6 356.8 0.42680 .95536 14.25 .0627
5 Feed 379.6 0.15285 .98755 14.34 .0699
4 387.6 0.04343 .99763 14.43 .0723
3 390.2 0.01103 .99919 14.52 .0731
2 391.1 0.00265 .99981 14.61 .0734
1 Reboiler 391.7 0.00056 .99996 14.70 .0736
Material Balance
Components FeedMoles a
Top Product Moles Bottom Product Moles
Ethanol 0.000085 .000085 .000000

Ethylene glycol 3.499999 .000006 3.499993
Water 0.143586 .143442 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 Time
Top load 2,8709 B t u / U n i t Time
a
Based on one mole of feed to the extractive distillation column which precedes
the solvent recovery column.

Figure 7. Temperature 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 .

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 1
MOLE FRACTION
Figure 8. Composition profiles for solvent recovery column
Stripping water from aqueous ethylene glycol

Table VIII. Comparing Extractive and Azeotropic Distillation
Feed: Aqueous Ethanol (85.64%m Ethanol)
Extractive Distillation, 14.7 psia Azeotropic Distillation, 50 psia
S o l v e n t = ethylene g l y c o l Entraner = n-pentane

M o l e s s o l v e n t - e t h a n o l = 4.08688 Moles n-pentane-ethanol = 3.214
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 . 18 T r a y s t o t a l i n azeotropic dist. c o l .
S o l v e n t o n t r a y 43 Entraner o n t r a y 18
F e e d on t r a y 22 F e e d o n t r a y 16
R e b o i l e r l o a d = 20.9 m i l l i o n R e b o i l e r l o a d = 10.7 m i l l i o n
Btu/hour e Btu/hour
T o p l o a d = 13.12 m i l l i o n C o n d e n s e r l o a d 11.33 m i l l i o n
Btu/hour Btu/hour
T o w e r d i a m e t e r = 5.3 feet T o w e r d i a m e t e r < 5 feet
Ethanol product: Ethanol product:
W a t e r 16 p p m (mole basis) W a t e r < 3 p p m ( m o l e basis)
S o l v e n t 1.2 p p m (mole basis) n - P e n t a n e < 1 p p m (mole basis)
E t h a n o l recovery f r o m feed = E t h a n o l r e c o v e r y f r o m feed
99.99% >99.99%
S o l v e n t recovery c o l u m n Stripping column

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
R e b o i l e r l o a d = 9.33 m i l l i o n Reboiler load <2. million
Btu/hour e Btu/hour
T o p l o a d = 8.11 m i l l i o n Top load <2. million Btu/hour

Btu/hour
T o w e r d i a m e t e r = 4.1 feet T o w e r d i a m e t e r < 2 . feet
T o t a l heat to reboilers = 30.23 T o t a l heat t o reboilers < 13 m i l l i o n

million Btu/hour Btu/hour
T o t a l t o p loads = 21.23 m i l l i o n T o t a l t o p loads < 14 m i l l i o n
Btu/hour Btu/hour
"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.

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 extrac-
t 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 process-
i 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, oper-
ates 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 X
M
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
(Li)a- 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 ordi-

nary distillation for the separation of propylene-propane
mixtures. Varticular attention is given to the necessary com-
promises between different design factors: solvent concen-
tration 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 dis-
tillation attractive. It appears that in almost all cases extrac-
tive 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 considered

* 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 d i s c u s s i o n identifies
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 t h e i r p o s s i b l e interactions.
S o m e of the design variables may h a v e synergistic effects i n terms of
s e p a r a t i o n cost w h i l e others m a y 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 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 pro-
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 for
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 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 Considerations 17
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 asso-
c 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 accept-
able 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

Solvent Propane
Product
Extractive Distillation
Feed
Column
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

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 A = (lny> )x A 8
2
l n y B = = (In y )xsB
2
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 generally
provides a good first-order 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
() (PA) RT)
" A B =
(y )
B (P%) ( 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
(4)
-(ft)
<*AB
where S = y A/y
= S
(x )
s
such t h a t f (x )
8 - 1 when x 8 1
and f (x )
8 < 1 for x 8 < 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 , as esti-
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 ) . 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 sepa-
r 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 a c t i v i t y coefficients could be
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. Tassios ( 2 ) 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
a c t i v i t y coefficients are those p r o p o s e d b y W e i m e r and Prausnitz (3)
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). 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 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-

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
y
2.2 X 2,2,3, Trichlorobutyronitrile y
y
y
y
2.0 y Gerster' Plot
Butyronitrilt Bostd on Dota for
Acrylonitrile y Ptfltant end Penttne
1.8 - X y
y
Acttone y
S Acetonitrilt
1.6 X Dota Quoted by
^ PrapiOMtril*
HofthMd
^ w i U M H 111 IB
' X
_ Furfural
1.4

y
1.2
0MF x
1.0 I 1 1 1 1 11 1 1 I l I I I
1 2 3 4 5 6 7 8 9 15 20 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

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.
(2) yc H8 w a s h e l d constant w i t h v a r y i n g values of S .
3
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.
yxA Am 1 (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-^) 2
+ 1^ (6)
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 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 solvent-
recovery 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 heat-
transfer 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 Considerations 23
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
Feed Rate = 415 l b m o l e s / h r

Composition = 50 mole % C H , 50 mole % C H ,
3 8 3
Condition = s a t u r a t e d v a p o r a t the tower

pressure"
Propylene Purity = 99.0%

Recovery = 95.0%
Capacity = 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 = ^ 0 . 0 1 mole %
N o r m a l boiling point = 140F
O t h e r p h y s i c a l properties = those of acetone
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 = 0.85 to 0.90 mole f r a c t i o n
S
= 1.7 to 3.1
yC3H8 = 6.0 to 16.0
Coolant Coolant = water
Inlet temperature = 70 F
T e m p e r a t u r e rise i n
condensers = 20F
M i n i m u m approach
temperature = 10F
Cooler/Process Heat Exchangers

M i n i m u m approach
temperature = 20F
" F o r binary distillation without solvent, the feed condition was taken as satu-
rated 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

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 en-

t 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 alter-
n 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 (9),
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) 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 ex-
p 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 re-
m 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 separa-
t 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

Table II. 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 = sieve t r a y s
costs = Peters a n d T i m m e r h a u s {12), F i g u r e 1 5 - 2 6 , p. 659
H e a t exchangers = floating-head, % - i n c h tubes, 2 0 - f t - l o n g b u n d l e
costs = 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
Utilities
H i g h pressure s t e a m (500 psig) = $1.00/10 6

BTU
L o w pressure s t e a m (100 psig) = S0.40/10 6

BTU
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 = Peters a n d T i m m e r h a u s

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

0.84 0B6 0B8 0.90
Solvent Mole Fraction on Solvent Addition Plate, x s
Figure 4. Effect of solvent concentration on the number of equi-

librium 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 .

Selectivity and A c t i v i t y Coefficients. 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 solvent-
flow 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 1400
c
t
1200
1000
tf-Total For
800 Fractional Distillation Fixed
Without Heat Exchange System
600 With Heat Exchange System
-L _L
400
0.84 0B6 0B8 0.90
Solvent Concentration, x e
Figure 5. Effect of solvent concentration on annual costs

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

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 solvent-

t 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.

Solvent
Propane Product
Extractive
Distillation
Feed Column
Solvent
Cooler
w
..Steam - 0
-Main
Bottoms
Column
Reboiler E3
Preheater Solvent
Recovery Propylene
Steam - - - - ( ) Column Product
Waste Hef Steam

Boiler Recovery Column
Reboiler
Figure 8. Extractive 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

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-
0 I I I I I I I
2.0 2.4 2.8 3.2 3.4
Selectivity, / .
C
3 8
H C
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

Solvent
E3 Propane
Product
Feed Extractive
Distillation
Column
Steam r^C^^ Solvent Propylene

1 >i ^ fFlosh \ Recovery Product
H^T^ D r u m Column
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

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 0 0
seems to be flattening out at S 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 8
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 e
8 w t % C H , 7 w t % acrylonitrile, 5 w t % water, a n d 1 w t % by-product

3 8
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 cis-
a 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 dis-
t 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 4 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 -

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 4 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 3
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 equi-
librium 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 sepa-
r 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

OVERHEAD
PRODUCT
REFLUX
AND
5 DISSOLVER
EXTRACTIVE SALT
DISTILLATION
COLUMN
SALT
FEED RECYCLE
BOTTOMS
PRODUCT
Figure 1. Flowsheet for extractive distillation using a dissolved salt

as the separating agent
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 separating
agent (the third component), 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
process. 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 Salt Effect 37
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. A
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 die
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. 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, some-
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. This
is because m u c h stronger forces of association w i t h f e e d 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.

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 satu-
ration 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

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, is for s a t u r a t e d p o t a s s i u m
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 concentrationi.e.,
its s o l u b i l i t y r a n g e s from 49 mole % 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 moderate
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 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 equilibrium data at atmospheric pressure for
the boiling ethanol-water system containing calcium chloride at con-
stant concentration

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 representa-
t 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 dis-
s 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 for
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. 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 when
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 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 cate-
gories: 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 electro-
lytese.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 -

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 compositionis
r e l a t e d to the degree of difference 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, 1- and 2-propanol-water, nitric acid-water,
acetone-methanol, 1-octane-propionic acid, phenol-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 by
F u r t e r (11). 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-

t i v i t y of each volatile component, 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, inter-
n 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

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 vapor
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 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. No
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. 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

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. Principal
developers of this process h a v e b e e n H e r c u l e s a n d Tennessee 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 reviewed
elsewhere (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 some-
times 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
DIMITRIOS P. TASSIOS
Newark College of Engineering, Newark, N. J. 07102
Rapid predictive and experimental techniques for screen-

ing 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. TASSIOS Extractive Distilfotion Solvents 47
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 a v a i l a b l e t h r o u g h t h e years. This paper
presents a r e v i e w o f some o f these m e t h o d s 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. 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
with ethanol, 1-propanol, a n d 1-butanol, acetone forms increasingly
n o n i d e a l solutions w i t h t h e m . 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.

Table I. Potential Solvents for the Acetone "-Methanol 6

Separation
Solvent B.P., C Solvent B.P., C
Methylethyl ketone 79.6 Ethanol 78.4

M e t h y l -propyl ketone 102.0 Propanol 97.8
M e t h y l i s o b u t y l ketone 115.9 Water 100.0
M e t h y l n - a m y l ketone, etc. 150.6 Butanol 117.0
A m y l alcohol 137.8
Ethylene glycol 197.4
"Boiling point: 54.6C.
b
B o i l i n g point: 64.7C.
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 estab
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, 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-alco-
hols 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 ) d a t a of W e h e a n d
Coates (6). 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 values are u s e d w i t h equations l i k e those of V a n L a a r
or W i l s o n (7) 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 (x-t/
c u r v e close to t h e 45 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 relative
v o l a t i l i t y to invert. Scheibel (3) recommends 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 mix
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 ) and Weimer
a n d P r a u s n i t z (10). 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
(II), 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. TASSIOS Extractive Distillation Solvents 49
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 re-

r 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 (13),
a n d D e a l a n d D e r r (14) 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
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) are p r e s e n t e d a l o n g w i t h the values
for 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 I I I I I I I I I I L
5.0 6.0 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

( 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 ,

2
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 solvents
acting as electron acceptors (Lewis acid). The hydrocarbon that
forms the m o s t stable c o m p l e x w i t h the solvent experiences a decrease
i n volatility. E l e c t r o n donors are r a t e d b y ionization potential, and
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 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 (9).
While data on ionization potentials of hydrocarbons can be found
(15, 16), 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 (8) recommend
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), b e u s e d to 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 (18,
19). 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 (96.5%
Table II. Selectivities and Polar Cohesive Energy Densities for the
Hexane ( l ) - B e n z e n e (2) System at 25C (12)
Solvent S2J T (cal/cc)

t
m
M E K 3.6 5.33
Acetone 3.8 6.14
Pyridine 5.2 3.71
Aniline 12.2 6.37
Acetonitrile 9.4 8.98
Propionitrile 6.5 7.17
Nitromethane 15.0 9.44
Nitrobenzene 5.8 4.89
Phenol 6.0 9.84
Furfural 10.9 7.62
Dimethyl-sulfoxide 22.0 9.47
D i m e t h y l formamide 12.5 8.07

1.4

-
1.2
-
1/1

1.0

0.8

0.6 -

1 1 I 1 I 1
20 40 60 80
I g.molel
Figure 2. Variation of selectivity with solvent's polar cohesive density;

system: hexane (l)-benzene (2) at 25C (12)
weight furfural and 3 . 5 % water). H o w e v e r , G e r s t e r et al (22) report

that selectivity 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 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 2 H e n c e , as X i decreases, i2 increases
more rapidly than w h e n x 2 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

Solvent Mole Fraction

0 0 0.2 04 06 08 1 0
0.0 02 0.4 0.6 0 8 1.0

Solvent V o l u m ^ y d r e e V o |
Figure 3. Variation of refotive volatility with solvent amount.

Hydrocarbon ratio is 1:1. P: Constant.
ethylcyclohexane (l)-ethyl 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 (19). A s the r a t i o

(xi/xo) 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 4 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
(25) 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:

d(logS ) 12 _ L \ - L \
tf(l/T) ~ 2.303R v
'
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
k
t i o n i n the solvent.
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 )2
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 ) .
30
i.ol I I I I 1 1 1
0.0 02 04 0.6 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

Table III. Selectivity of Pure and Mixed Solvents
Mixed Solvents
Solute B; Vol% sa
M e t h y l Cellosolve Nitromethane 0 1.69

n-Pentane(3) Pyridine -Butyrolactone 0 1.60

Pyridine -Butyrolactone 32.1 1.79
1-Pentene(2) Pyridine -Butyrolactone 100 2.17
E t h y l m e t h y l ketone -Butyrolactone 100 2.17

Acetonitrile Water 0 1.64

P r o p a n e (3) Acetonitrile Water 50 1.34
P r o p y l e n e (2) Acetonitrile Water 100 .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). 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
method (4), the p a r a c h o r m e t h o d (27), a n d the Weimer-Prausnitz
method (10), modified by Hellpinstill and V a n Winkle (28). Since
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 a n d noninfinite dilution condi
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 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 x a n d n^). F o r the
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 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 2
log o y x _ A + l l + B 2 ^ + ^ + Dofa-n*)* (5)

n2 no U\
w h e r e the constants are functions of t e m p e r a t u r e , B 2 and F 2 are f u n c t i o n s

of t h e solvent series, C x is a f u n c t i o n of the solute series, A lt2 is a f u n c t i o n
of b o t h , a n d D Q 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 coeffi
cient. So for -alcohols i n w a t e r :

4. TASSIOS Extractive Distilhtion Solvents 55
l o g y\ = + B % + 2 CJn x (6)
Notice that the t e r m D 0 (%-n ) 2

2
was i n c o r p o r a t e d i n t o the
constant because D G 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. B 2 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 fixed
solvent. F o r unalkylated cyclic (aromatic and/or naphthenic) hydro
c a r b o n s i n fixed solvents:
log y\ = + Bn a a + Bn n n + C [l/r -r 1] (8)
where Ba and B n are solvent dependent constants, C 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 a 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
bers, respectively. 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 n + 1.845[l/r - 1] (9)
30 I ~ 1
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

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 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
V
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.
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

2
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

2 - 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. TASSIOS Extractive 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 2 - [( -
2 )
2
2
+ 2
- 2 ]
12 +
RT[ In V / V i +
2 1 - V2/V1] (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 2
(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 o 2
-V [(Ai - )
2 2
2
+ ( - *) -2
2 ]
12 +
R T [ l n V2/V1 + 1 - V2/V1] (13a)
A l s o E q u a t i o n 14 b e c o m e s :
12 = 1(1 - )
2
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. 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
Table IV. T h e values for are t a k e n f r o m plots ( 2 8 ) .
{ The method for
c a l c u l a t i n g ^ is also a v a i l a b l e (28).
T h e term 12 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 ) is o n l y u s e d
to screen; the s e c o n d (36), besides screening, gives infinite d i l u t i o n r e l a
tive volatilities. B o t h methods r e q u i r e a solvent w i t h a l o w e r vapor
pressure t h a n the solutes as i n extractive d i s t i l l a t i o n .

Table IV. Values for k in Equation (14a)

% Average Absolute
System k Error in
Paraffins 0.399 11.6

Olefins 0.388 8.5
Aromatics 0.447 13.5
Screening Solvents through G L C . I n g a s - l i q u i d chromatography

(GLC) separating mixture components is b a s e d o n the p a r t i t i o n i n g
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 strengths w i t h t h e m , a l o n g
w i t h t h e v a p o r pressure differences. 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 = D />i2 (15)
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 Solvents 59
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 12 (max). 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 ) that
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 relative
volatility:
<x ij = (16)
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 each
solvent u n d e r c o n s i d e r a t i o n , a tedious project. A y e a r l a t e r Sheets a n d
M a r c h e l l o (38) 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 0.03 gram moles Sec

12
Pyridine 3.70 5.85 5.40
Propionitrile 4.80 6.10 6.40
Furfural 6.55 6.40 7.50
Nitromethane 7.00 6.95 7.95
N-methylpyrrolidone 8.20 8.40 8.40
Diethyleneglycol 9.10 4.70 4.50
a
Calculated for two solvent amounts.

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 .
4
1 3 5 7 9 C*2
Figure 7. Relationship
Hydrocarbon Processing
between maximum separation factors and
infinite dilution rehtive volatilities for the system: n-hexane-benzene
^
with various solvents at 67C (35)

Figure 8. Variation of selectivity with solvent's polar cohesive

energy density
propane (l)-propene (2) at 27C (24)
pentane (l)-pentene (2) at 25C (10)
J . butyronitrile 2. acetone 3. propionitrile
4. acetonitrile 5. furfural 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 -

served. 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), 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
mended. 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. The Helpinstill-Van
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 over t h e W P method. Recently,
N u l l a n d P a l m e r (43) 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). 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
expected. 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
mended (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 separable
v a p o r a n d l i q u i d phases. 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, A N D DITSLER Computer Calcufotions 65
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
0
(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.

Phase 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 three-
phase 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, A N D DITSLER Computer Calculations 67
T h e f u g a c i t y coefficients 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 2

[SGW 2
-
(XGvY,)*-] + (P/2.3R T ) [27,(1 -2 2
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
_ (y^\ [(y -X )Tj+

i i (Xj-xjyn /P,flA ( R .
" li
\ W [to - Xi)T< + (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 . ForSOLTER and 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 give the
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 are calculated for both

programs. 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 (6).
Azeotropic 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. Twenty-one D A T A cards a l l o w the user to g i v e
the pertinent conditions 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 stage-
by-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, x9
h Y h , , 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 . H o w e v e r , it
does t r y via 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 liquid
phases are e x p e c t e d o n the trays. The 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 phase
appears. 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.

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. 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
ADPLLE. 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 balance
is satisfied w h e n the entire aqueous phase is r e m o v e d . A s the c a l c u l a t i o n
proceeds 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 a
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

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 % ethanol.
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. 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 vapors to
13.85 m o l e %.
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 mole
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 i n the bottom product,
e t h a n o l ; this has b e e n set at 0.62 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, i n t h e s t r i p p e r bottoms re-
f e r r e d to as D I S T I L L A T E . 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 Calculations 71
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. T h e first four pages
describe the features of the p r o g r a m . 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 . The thermo-
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-to-
stage 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 a 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 frac-
t 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. Also
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 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 .

Table I. Ternary Azeotropic Distillation Program ( A D P / A D P L L E ) to
TERNARY AZEOTROPIC DISTILLATION PROGRAM (ADP/ADPLLE)
THIS PROGRAM USES A SPECIAL SYSTEM OF UTILITY SUBROUTINES! W J T H PROGRAMMED INITIALIZATION AS FOLLOWS Computer Output Page 1
THESE CONTROL OPTIONS ARE AVAILABLE.
KNTRL 1) 3 1 ADP PROGRAM

KNTRL 1) a 2 ADPLLE PROGRAM
KNTRL 1) 8 3 C O M B I N A T I O N OF A D P / A O P L L E PROGRAMS
KNTRL 2) s 1 SYSTEM 1
KNTRL 2) 2 SYSTEM 2
KNTRL 2) 8 S SYSTEM 5
KNTRL 2) g 6 SY5TEM 6
KNTRL 2) 3 7 SYSTEM 7 PNTANj.>ETHMOL-VfATE
KNTRL < 2) S SYSTEM
KNTRL < 2) 8 9 SYSTEM 9
K N T R L *< 2) 8 3,0
KNTRL < 2) 8 11 SYSTEM 11
KNTRL 2) 3 12 SYSTEM i2
KNTRL 2) S 13 SYSTEM 13
KNTRL 2) S 14 S Y S T E M 14
KNTRL < 2) a 15 S Y S T E M i5
KNTRL 2) 8 16 SYSTEM 1 6
KNTRL 2) a 17 S Y S T E M i7
KN RL
T < 2> 3 18 SySyEM 1 8
KNTRL < 2) 3 19
KNTRL < 2) 8 20
KNTRL 2) S 21 LO D
A -L C O M P O N E N T
FROM CA F!.)S f-TFR
A UTILITY OAT A
KNTRL 3) 3 1 SET C0MP<2> SOMTFNT IN T O P S VAPOR

KNTRL 3) 3 2 SET CMP(3) IN REFLUX

M
KNTRL 4) a 1 SET F E E D TRAY AT SAME C O M P ( 2 ) / C O P ( 3 > *AT10 A S FEEO
KNTRL < 4) a 2 SET F E E O T ^ A V 3Y D A T A CARD INPUT <D(l2>)
KNTRL ( 5) 3 1 ACCUMULATOR CALCULATION ISOTHERMAL (IF KNTRL(D*2 3)

KNTRL < 5) 3 2 ACCUMULATOR CALCULATION ISOBARIC (IF KNTRL(D2 3)
KNTRL ( !>> 3 3 ACCUMULATOR MOT C A L C U L A T E D

KNTRL 6) e 1 MEATER/SUBCOOLER PRESENT (lp KNTRL(5)1 2)
KNTRL < 6) s 2 HEATER/SJBCOOLER MOT PRESENT
KNTRL 7) 3 1 STRIPPER NOT P R E S E N T ( M U S T SET D(2() IF KNTRL(1)2 3)

KNTRL < 7> 3 2 STRIPPER 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)
KNTRL 7) 3 3 STRIPPER 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)
KNTRL ( f t ) * 1 PRINT A L L COMPONENT DATA
P N NJ A T A
KNTRL < C) s 2 SUPPRLKS P R A T I N G OF A L L C M O E T o
TMESE QUANTITIES ARE BUILT INTO THE PROGRAM AS PARAMETERSi BUT THE VALUES MAY BP CHANGED BY THE USER Computer Output Page 2
THROUGH THE USE OF PPMTR-CAROS.
MAX CYCLESUF KNTRL(1>2#3 AND KNTR^(7)sj.) ( ) f,0

MAX CYCLES(JF KNTRL(l)s2.3 AND KNTR.(7),2> Pt 2) - *,0
FEED TRAY DISPLACEMENT(ONLY IF KNTRL()=3) PC 3> 3.0
MAXIMUM AQP PASSES ALLOWED (IF KNTRL<1>3> Pt 41 25.0
THESE UUAf-iTlTlES ARE TO BE SUPPLIED BY THE USER BY MEANS OF DATACARDS. Computer Output Page 3
1 )
D( = FEED C0MP(2) MOLFS/HR FORMAT E15.8
2) FEED I ON
C0MP2) MOLE FRACT FORMAT E15.8
FORMAT
D< * FEED TEMPERATURE (SUBCOOLEO Lieuip)
F^RENHEH Eis.e
PRESSEE FORMAT
D< 3) REBOILER
PSIA E15.8
FORMAT
D( 4)* PRESSURE DROP PER TRAY PSIA
D( 5) REFLUX TEMPERATURE FORMAT
15.8
D( 6) FAHRENHEIT E15.8
S FORMAT
D< 7) REFLUX CMP(3) MOLE F R A T I 0 N
C < I F KNTRL<3)2> gl5.8
FORMAT
D( ft) REBOILER VAPOR MOLES/HR E15.8
FORMAT
D( 9)* BOTTOMS COMP(l) MOLE F R A CTTION 15.8
T FORM T
A
D<10> * PTTOMS B MP(3) C
MOLE F R A C I ON 15.8
D<1D s TOPS VAPOR 0cOMP(2) ( I F KNTRL(3)1)
MOLF I ON
FRA T C
FORMAT
15.8
D(12) * FEED TRAY LOCATION (IF KNTRL(4)2> FORMAT 15.8
MOLE FRACT ION FORMAT
0(13) r DISTILLATE COMP(l) 15.8
MOLE FRACT I ON FORMAT
D(14) * DISTILLATE C0MP2) E15.8
MOLE FRACT ION FORMAT
D(15) = DISTILLATE C0MP(3) 15.8
n<16) FEED 8
MOLe FRArT
0 M P (
ION FORMAT
C *> R
(D I F KNTRL(5)P2> FORMAT
T
ii5.8
0(17) ACCUMULA OR yEMPERATUT f FAHRENHEIT
D(lh) (IF K N T R L ( 5 ) 2 ) FORMAT E15.8
DP (TOP PRESS-AC PRESS) P S H
D(19) ( I F KNTRL(6)1) FORMAT E15.8
HFATER/SUBCOOLER TEMP FAHRENHEIT
Q(20) R Y
( I F KNTRL(7)1) FORMAT FlO.l
NUM E
8 F C C L E S FOR A L L E D
D(2D TOLERANCE OF C0MP<7> AND CftMPO) (IF KNTRL(7)2) FORMAT E15.8

DESCRIPTIVE IDENTIFICATIONS HAVE BEEN ESTABl 1SHED FOR THESE VARIABLES. Computer Output Page k
FEED MOLES/HR FORMAT 15,8

1) COMP(l)
FEED C0MP(2)
V( s
V( 2) MOLES/HR FORMAT 15.8
FEED C0MP(3) MOLES/HR FORMAT 15.8

V( 3) FEED TOUL MOLES/HR FORMAT E15.8
V( 4)- BOTTOMS MOLES/HR FORMAT E15.8
V( 5) BOTTOMS (,OMP{
C0MP(2 i )) MOLES/HR FORMAT 15.8
V( 6) BOTTOMS C0MP(3) MOLES/HR FORMAT E15.8
V< 8)
V( 7) BOTTOMS TOTAL MOLES/HR FORMAT 15.8
DISTILLATE MOLES/HR FORMAT 15.8
V
v(
d o )9)s DISTILLATE COMP(1)
C 0MP(2) MOLES/HR FORMAT 15.8

V<11> * DISTILLATE cOMP(3> MOLES/hR FORMAT 15.8

V<12) DISTILLATE TOTAL MOLES/K& FORMAT 15.8
V(13) * COMP(l) VAPOR-LIOUID FLOW STRIPPING SECTION MOLES/HR FORMAT 15.8
V(i4) 2
COMP( ) VAPOR-LIOUID F L O STRIPPING SECTION MOLES/HR FORMAT
w E5,8
V(15, COMP<3) VAPOR-LIQUID FLOW STRIPPING SECTION MOLES/HR FORMAT E15.8
T
V<16) * H E A FLOW STRIPPING SECTION /HR FORMAT 15.8
T
V<17) 0MP<1) VAP0R-LiQU, OW R I F Y I N G S T i O N MOLES/H* FORMAT 1 5 . 8
C n FL E C EC E
V(18) * COMPi?) VAPOR-LIQUID FLOW RECTIFYING SECTION MOLES/HR FORMAT 15.8

( 9) W
* COMPt 3 ) yAPOR-LIOUlO FLO RECTlFylNG SECTION MOLES/HR FORMAT Ei5.8
V(20, HEAT FLOW RECTIFYING SECTION BTU/HR FORMAT 15,8
V(21> * VALUE OF D(1C> WHEN KNTFL(1>3 FORMAT 15.8
TERNARY AlEOTROPIC DISTILLATION PROGRAM ( A D P / A D P L L O Computer Output Page 5
RUN NO 9 9 TEST OF AQP/ADPLLE OPTION KNTRL(1>3
THE" CONTROL OPTIONS HAVE BEEN S E T AS FOLLOWS
KNT^L ( 1) C O M B I N A T I O N O F ADP/ADPLLE PROGRAMS

KNT^L ( 2) SYSTEM 7 3NTAN2-ETHNOL-WATER
KNTRL ( 3) S T cChP(2) ; C M T K T I N T O P S VAPOR
T R
KNTRL < 4> 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
A
w
KNTRL < b) ACCUMULATOR CALCULATION ISOTHERMAL ( I F KNTRL<1>23)
E
KNTRL ( 6) HE ATFR/S.jBCOOL N N T P R E S E N T
KNTRL < 7) 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>
KNTRL ( t) P R I N T A L L COMPONENT DATA
>

THE FOLLOWING DATA A P EUSED FOR THIS CALCULATION
FE0 COMP(?) MOLES/MR 0 ( 1> .24202000*03

FEE" COMP(2) h OLE FRACT I ON 0( 2 ) .85640000*00
FEEO TEMPERATURE FAHRENHEIT (SUBCOOLED L I Q U I D ) 0( 3 ) ,11000000*03
REBILEP PRESSURE PS I A Oi 4 ) .50000000*02
P R E S S U R E DROP P E R TRAY PSIA D( 5 ) .14000000*00
REFLUX TEMPERATURE FAHRENHEIT 0( 6 ) ,15445000*03
T .34999999*01
REFLUX OMP<3> MOLE F R A C I 3 N
C
( I F KNTRL(3>2> 0< 7 )
U .80000000*03
R E B I L E P VAPOP MOLES/HR

MOLF. F R A C T I
o( a) ,61999999-06
BOTTOMS COMP(i) 0( 9 )
MOLE F R A C T I ,25560000*03
BOTTOMS COMP(3) 0(1C)
MOLE F R A C T I (IF KNTRL(3)1) .13850000*00
TOPS VAPOR C0MP(2) 0 ( H )
(IF KNTRL<4>2> .15000000*02
F E E D TRAY L O C A T I O N 0(12)
MOLE FRACTI ON .99999999* 50
DISTILLATE COMPtj)
MOLE FRACTI DN ,89999999*04
DISTILLATE C0NP{2) 8! .99990000*00

DISTILLATE tOMP<3) MOLE FRACTI ON 0(15)
MOLE FRAT1 .00000000
FEED COMP(l) ON 0(16)
.15445000*03
ACC M ,LA OR E M P E R A R E FAHRENHEIJ
L ) L T T T U
<'T F K N T R L ( 5 > 2 > D(17>
,00000000
DP ( T O P P R E S S - A C P R E S S ) PSjA ( I F KNTRL(5)i2> 0(18)
.00000000
HEATER/SURCOOLER TEMP FAHRENHEIT ( I F KMTRL(6)sl) 0(19)
.0
NUMftER OF C Y C L E S F O R A D P L L E (IF KNTRL(7)1) 0(20)
R mP (IF KNTRL(7)t2) .00000000
T O L E A N E OF C < 2 > ANp f.0MP<3)
C 0 (2l)
AZEOTROPIC DISTI.LATION PROGRAM (APP'A3PLLE>
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.
ISOTHERMAL ACCUMULATOR CALCULATION
TEMP 154,430 F
HEATER/SUBCOOLER NOT PRESENT
STRIPPER PRESENT
RUN CVCLES - 1
AI J A JI CU TEMP
.93892120-00 .92929000-00 .17486900-00 75.000 C PNTAN2-ETHN0L
.41365440+01 .24165000*01 .29700000-00 75.000 C PNTN2-WATER
.72799999-00 .40700000-00 .00000000 75i00Q C EfHNOtATER
AI J AJI CJ TEMP 1- J
.88388000-00 .87359000-00 .15507600-00 87,800 PNTAN2-ETHN0L
.39480000*01 .22125185*01 .25800000-00 87,800 PNTAN2-WATER
.40080000-00 .00000000 87.800 ETHNOL-WATER
.74600000-00
AI J AJI ciJ TEMP I J
.83367725-00 .82406500-00 .13747500-00 lOOtOOQ PNTAN2-ETHN0L
. 77 936* i 22500000*00 PNTANs-WATER
3 l 2 0 2Q3noooo*oi
,76050000-00 .00000000 ETHNOL-WATER
.39250000-00
7 CLASSES
B
COEFFICIENTS FOR VAPOR R?SSURE EQUATIONS
PNTAN2 .226933*02 ,208645*04 ,273160*03 ,525l7o*01 ,159785*01 .0000
.816290*01 .162322*04 ,228980+03 .000000 , .0000
ETHNOL
.208440*02 ,28i740*04 ,273160*03 ,404859*01 oooooo .0000
WATER
TC PC ATMS C4I CC/GM EPR AMPR

.470300*03 ,331000*02 ,141000*03 ,000000

PNT N2 A
oooooo
ETHNOL .516300*03 ,631000*02 ,759000*02 .890000-01 475000*01
WATER .647000*03 ,218000*03 ,247000*02 .260000-01 .475000*01
TEMP F L I O BTU/ÔL VAP BTU/MOL
PNTAN2 100.000 39682500*04 ,55500+5
PNTAN2 200.000 ,82972500*04 ,17748900*05

PN AN2 30000 .132756 *Q5
0 C .'20346300*05
T
ETHNOL 100.000 .25061000*04 .20 37 00+05

9 9
ETHNOL 200.000 ,60349000*04 ,22573300*05

ETHNOL 300.000 .10365300*05 .23969200*05
100.000 .12250000*04 .19916000*05
WATER
200.000 .30270000*04 .20649000*05
WATER
300,000 ,48200000*04 .21290001*05
WATER
LIQUIO ENTWALPr EQUATION COEFFICIENTS VAPOR .-
PNTAN2 288600+03 335498*02 324675-01 ,125541+05 25974 *02 ,372529-08 ( 0
ETHNOL -'.221100*03 '.232640*02 .400800-01 .190630*05 ,199465*02 *.119750*01

WATER -.566000*03 .l8l55o*02 -.450000-03 .l909lO*Q5 ,71000*01 .460000-02
PREl IMINAPY RESULTS FOLLOW Computer Output Page 7
PROGRAM HAS CALCULATED THE FOLLOWING VARIABLES
FEED COMP(l) MOLES/HR V< 1 ) -- .00000000

)
FEED C0MP< > 2
MOLES/HP V< 2

FEED C0MP(3) MOLES/HR V( 3 )
FEED TOTAL KOLES/HR V( 4 ) .28260159*03
BOTTOMS C0MP<1> MOLES/HR V( 5 ) .15005057*03
BOTTOMS COMP(2) MOLES/HR V( 6 ) .24201635*03
BOTTOMS C0MP<3) MOLES/HR V< 7) .56181042*03
BOTTOMS TfTAL MOLES/HR .24201705*03
DISTILLATE COMP(l) MOLES/HR V<

9) .40584534-03
R
DlSTiLLAT E 0MP(2)
C MOLES/H .36526080*02
mo> .40580475*02
DISTILLATE C0MP(3) MOLEE/WR VUl>
DISTILLAIE TOTAL MOLES/HR W12) .40584534*02
VALUE OF D(10> ^ H E N KNTPL<1>3 VUl> .23213671*05
Computer Output Page 8
REBOILER PRESSURE* 50.00C TEMPt 234.910

C0*P VAPOR M/HR L.!0 M/WR LIS BTU/M VAP BTU/M VP/THETA X <01> ..ALPHA GAMMA THETA
PNTAN2 ,0059 ,0061 9961,3993 18655,6430 98,3158 ,000006 ,000007 11,947562 6,076075 1,144542
FTHNOL 799.992C 1042.0083 7455.5545 23087.8140 49,9997 ,999992 ,999990 1.000000 1,000000 ,999999
WATER .0021 .0026 3653.9526 20883,2230 23,1712 .000003 ,000003 1.116915 2,410122 ,983621
TOTAL 800.0000 1042,0l70 7768820.1 18470220,0
w T e S S )
MOLE FACTION A E * <ENTR tNER F ^ E 3 A 1 A
,000003 ,000003
KTRAYs J PRESSURE* 49.860 TElPe 234.74P M 2 N 5 *NTRL<10 )

CONP VAPOR M/MR LlQ M / H R LIQ / VAP TU/M B VP/THETA X ( 2) Y ALPHA GAMMA THTA

PN AN2
T ,0558 .0559 9944.2387 j865.454 0 98.421 000054 00007o 11 9 8 9 7 7 1 6,70 .146420
FTHNOL 799,1022 1C41.U86 7440.7544 23085,5050 49,8567 ,999944 ,999927 1.000000 i,000000 ,999994
WATER .O0 3 .00 e 23647.64i7 2 2088 .670
2 230 0
2 .OOOOO3 ,000003 24l0589 983646
11
TOTAL 799,1602 1041,1773 7747273,7 18448765,0
MOI FRACTION V TER (ENTRAINER FREF BASIS)
A
,000003 ,000003
KTRAYs 2 PRESSURE^ 49.7 0 TE^P 234.558 2

M 2 6

KNTRUiOi
COMP VAPOR M/HR LIO M/HR LIQ BTU/M VAP BTU/M VP/THETA X < 3) Y .ALPHA GAMMA . TMTA
PMTAN2 .5139 ,5i41 9921,9861 18646.5080 97,9429 .000494 ,000644 11,993293 6,004698 1,146209
FTMNOL 797.7091 1039,7 54 7421.5674 2 2308?,776o 49,6905 .999503 ,999353 1,000000 1,000000 ,999943
WATER .0024 .0030 3639.4535 20880.9200 23,0212 .000003 ,000003 1.11774 2.41380 ,913646
TOTAL 798. ?54 22425 77 5 34 2 0 2 2
84 97 2
MOLE F R A C T ON WA ,000003 ,000003
KTRAY* 3 PRESSURE* 49.580 TEMP : 234.102 M 2 N 6 KNTRL(10)
LIQ M/HR LIQ BTU/M VAP BTU/M VP/THETA X ( 4) Y .ALPHA CAMMA THBTA
COMP V POR M/HR
A
4,6852 4.6854 9783.6962 18634,6550 97,5110 ,004529 ,005912 12.028157 6.0826O6 ,145188
PNTAM2 1,000001 ,999483
ETHNOL 787,8411 1029.8574 7302.4418 23076,2360 49,3110 ,995468 ,994085 1.000000
.0025 .0031 3588.4516 20877,9290 22,8338 .000003 ,000003 1.118356 2,415163 ,913429
WAT R
E
TOTAL 792.5288 1034.5459 7566325.Q l8267766i0

MOLE FRACTION UAT R E (ENTRAINER FREE BASIS) ,000003 ,000003
M 3 5 *NTRLU0)
KTRAY* 4 PRESSURE* 49.440 TEMP* 231.260 THETA
COMP VAPOR M/MR LIQ M/HR LfQ BTU/M VAP BTU/M VP/THETA ( Y ALPHA GAMMA
PNTAN2 39,8050 39 8n52 0858,5103 f
1856 8360 95,0046 ,0397o ,052418 12,158900 6,023060 1,137047
<
ETHNOL 719,5733 961.58 >6 6510.6443 23035!3850 47,0586 ,960247 947579 1.000000 1,000061 ,999859
WATER .0024 ,0030 3241,9305 20859,2590 2.7125 .000003 ,000003 1,120858 2,446777 ,981333
TOTAL 759.3808 1001.3978 6613192.3 17314512,0
T N W T R S S > .000003 ,000003
MOLE FRAC IO A E <ENTR IN R
A E FREE B A I
8
KTRAY* 5 PRESSURE 49,300 T E M P 211.961 Me 3 5 *NTRL'<0 0
rOMP VAPOR M/HR LlQ M / H R LIQ BTU/M VAP BTU/M VP/TH TA
E ( 6) .ALPHA cAMMA TwiTA
18059.5690 78,7405 ,260787 ,341087 12,505131 9,372543 1,00*142
PNTAN2 268,0904 268,0906 7318,0396
2275 ,72 0
33,6685 .739211 ,6589|i i,004769 .97059
ETHNOL 5i7,8967 759,9^ 52i3.8 5 2 0
20730,5130 15.609 ,000002 ,0000 2,.751069 ,969674
WATER ,0020 ,0026 2*42,8492
TOTAL 785.9892 1028,0062 5923958.0 16625276,4
5 .000003 ,000004
MOLE FRACTION WAT R E ( NTRAIN R FR E
E E E =}A lS>
KTRAY* 6 PRESSURE" 49.160 T *p 178,640

E
3 " 5 KNTRL'(O)-
0MP
C V POR M / H R
A
L I Q M/HR LIQ BTU/M V P A BTU'M VP/ X ( 7) Y ALPHA GAHM A TMBTA
PNT N2
A 656.3955 656,3956 6^94.4591 17194,0960 54,1901 .550284 ,690351 6.319559 2.40460 1,010203
FTWNOL 294,4158 536.4321 4862.3906 22244,0940 17,5479 .449714 ,309646 1.000000 1.173503 ,947050
WATER .0022 .0028 2472.8385 20500.1590 7,5945 .000002 ,000002 2.225791 6,035234 ,959809
TOTAL 950'8i35 192835 7338423 7835850
MOLE FRACTION NATR (ENTRANER F R E E 3ASIS) ,000005 ,000007
KTRAY* 7 PRESSURE* 49,020 TEMP* 169,194 M 3 N 3 KNTRL(O> 0
VAP BTU/M VP/THETA X ( 8) Y ALPHA GAMMA THETA

COMP VAPOR M/HR LIQ M/HR LIQ BTU/M
PNTAN2 792,9419 792.9420 6817,9567 16948,7490 -48,2035 .631133 .7874 2.926727 1,444620 ,QQ17_
735
ETHNOL 221.4156 463.4319 47$9|i707 22095,0280 14,3011 .360863 ,218201 1.000000 l|663730 ,944806
WAT R ,0050 ,0056 2441.8741 20432.9990 6,1290 ,000004 ,000005 4,413907 17,43143 ,939835
E
TOTAL 1014.3625 1256.3795 7630346.8 l33l659,0

M0L FRACTION VATER (ENTRAINER FREE BASIS}
E
,000012 ,000023

KTRAY* s PRESSURE* 48.880 ^ 167.474 M 2 7 KNTRL'tO
CO 1 VAPOR M/HR LIQ M/HR L I Q BTU/M VAP BTU/M VP/THETA X ( 9) Y ALPHA GAMMA THETA
PNJTAN2 824,6641 824,6642 6797,2936 16904,0770 47 540 ,649058 ,801782 2,364207 1,316007 ,998997
ETHNOL 203.8620 445.87S3 4782.087 22067,6550 13,7553 .350932 ,198205 1.000000 ,909471 ,945259
WATER .0131 .0137 2433,4969 20420,6820 5,8866 .000011 ,000013 5.320614 23,775542 ,960337
TOTAL 1028,5392 1270.5562 7737756.5 18439207,0
MOLE FRA TJ0N WAT R ( NTRAIN R F*E? BASIS)
C E E E
,000031 ,000064
78 EXTRACTIVE A N DAZEOTROPIC DISTILLATION
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FTHNOL 191.0646 433.1010 4579,5937 22031.7840 13,0792 .342798 .187079 1.000000 1,989408 ,943163
WATER 9,1057 9, 62 2382.9789 0 20404,5470 3,5864 ,007208 ,008915 5.695273 26,327143 ,9*0408
TOTAL 1021.4107 1263.4277 7528436.8 18229770.0
MOLE FRACTION WATER (ENTRAINER FREE BASIS) ,020595 045485
NEXT TRAY IS FEED TRAY
8
KTRAY=16 PRESSURE 47.760 TE^P" 164,203 M 3 4 KNTRL<10) 0 r .
/
C 0MP VAPOR M/HR LIQ M/HR LIQ VAP TU/MB Vp/T&Et* X (7 Y ALPHA GAMMA TgfT*
PNTAN2 805,1856 05,1857 6581,6141 16819,1180 45,0731 .643332 ,797334 2.327323 .3016* ,991*23
ETHNOL 182,4605 424,4768 4604,3625 22015,40*0 trJW ,339151 ,180731 1,000000 1,968342 ,44073
WATgR 21.9231 21.9236 2345.7019 20397,1830 5,4569 ,017317 .0273 5,714574 26,369356 .939741
TOTAL I00'i569i 1251.5862 7305293.0 18006621.0
MOLE FRACTION WATER (ENTRAINER FRE5 3ASIS) .049112 ,1072*4
KTRAY*17 PRESSURE 47,620 TEMP. 162.i33 M 3 N 5 KNTRL'( io )

COMP VAPOR M/MR LIQ M/HR LIQ BTU/M VAP BTU/M VP/TMETA x ue> Y ALPHA GAMMA THfT*
PNTAN2 75?,29o5 750,2900 65o3 6753 f
16765 3520 43 8322 ,818033 .783370 2,471473 .322906 ,994187
ETHNOL 160.0411 160.0374 4540.*4524 21982,2030 12.2352 ,174487 67097 1.OOOOOO 1,917384 ,94370
WATER 47,4410 6,606 2313,8971 20382,2610 5,2050 ,007480 ,049333 5.739363 23,876892 .938201
TOT L A 957,7726 97,0 5622309,8 17063895,0
A S S )
MOLE FRA TjON WAT R ( NTRAiNF.R F * E E B I
c E t
,041106 ,228631
KTRAY18 PRESSURE* 47.480 TEMP* 160,367 M 1 N 5 KNTRK10)

COMP VAPOR M/HR LIQ M/wR LIQ BTU/M VAP BTU/M VP/THETA I9) Y ALPHA GAMMA TM1TA
PNTAN2 777,9226 777,9222 6244,8645 16719.4820 42,8265 .847792 ,811883 1.269234 1,100325
ETHNOL 130.7335 130.7 99 432*.1252 2 21953.799 0
11,7269 .142472 ,3644 1.000000 3,165983 94$9
WATER 49,5142 8,9337 2207,3051 20369,4990 4,9839 ,009736 ,031676 ,934943 3,815821 ,93942*
TOTAL 95,1704 917,5858 5443553,7 16885141,0
MOLE FRACTION WATER (ENTRAINER FREE BASIS ) .063966 ,274701
FINAL RESULTS FOLLOW Computer Output Page 1 1
PROGRAM HAS CALCULATED THE FOLLOWINS VARIABLES
FEED COMP(l) MOLES/HR Vt I t .00000000

FEED COMP(2> MOLES/HR V( 2) ,24202000+03

FEED C0MP(3) MOLES/HR VI 3 ) .405813884-02
FEED TOTAL MOLES/HR V< 4)
4 .28260159*03
BOTTOMS MOLES/HR Vt 5) .15005057.03
COMP(i)
BOTTOMS C0M(2> MOLES/HP V( 6) ,24201635*03
BOTTOMS COMP(3) MOLES/MR VI 71 ,5ei81042-03
BOTTOMS TOTAL MOLES/H" V( 8) a .24201705*03


DISTILLATE COMP(i) MOLES/HR V( 9 ) .40584334-03
DISTILLATE C0MR(2) MOLES/HR V(10> ,36526080*02
DISTILLATE C0MP(3) MOLES/HR vttr> .40380475*02
DISTILLATE TOTAL MOLES/HR VU2)
.40384534*02
C O M P ( i ) VAPOR-LIQIJIO F L 0 W STRIPPING SECTION MOLES/HR v t t 3 T *.15005057.03
C0MP(2) VAPOR-LIQUID FLOW STRIPPING S E C T ] t ON MOLES/HR VC14J -,242W*35*03
C0MP(3) V A P O R - L I Q U I O FLOW STRIPPING S E C T ] ION MOLES/HR V<15l .56181042.03
HEAT FLOW STRIPPING S Tl| iN C
BTU/HR V U 6 > .10701400*08
COMP(i) vAPOR-LIQijID FLO> REC-flFylNG S E C ON w T
MOLES/HR v U 7 > * .40584534*03
C0MP(2) VAPOR-LIQUID FLOW RECTIFYING SECT ON MOLES/HR V(18) ,36526080*02
C0MP<3) VAPOR-LIQUID FLOW RECTIFYING SECT ON MOLES/HR V U 9 > * .40580475*02
HEAT FLO RECTIF IN6 SECT ON w Y
BTU/HR v<20* " 144642*

VAPOR MOLES AND ENTHALPIES ARE FLOWS FROM THE TRAY
LIQUID MOLES A N D ENTHALPIES APE FLOwS TO THE TRAY
L I Q U I D AND VAPOR COMPOSITIONS ARE FOR THE FLOWS FROM THE TRAY
REBOILER PRESSURE 50.000 TEMP* 234,910

COMP VAPOR M/HR LIQ M/HR L I Q BTU/M VAP BTU/M VP/THETA X Y ALPHA GAMMA THETA
PNTAN2 .0059 ,QQ61 9961,3993 18655,6430 ,98315**02 000001 ,000007 .119476*02 .607608*01 .114654*01
ETHNOL 799.9920 1042.0083 7455.5545 23087,8140 ,499997*02 ,999997 ,999990 .100000*01 .100000*01 .999999-00
WATER .0021 .0026 3653.9526 2Q883.2230 .231712*02 ,000002 ,000003 .111692*01 .241012*01 .983621-00
TOTAL 800,0000 1042,0170 7768820,1 18470220,0
MOLE FRACTION ATER (ENTRAINER FREE 9ASIS)
W 000002 000003
KTRAY* 1 PRESSURE* 49,860 ** 234,748 Me 2 N 5

COMP VAPOR M/HR LIQ M/HR L I Q BTU/M VAP BTU/M VP/THETA X Y ALPHA GAMMA THETA
PNTAN2 .0558 ,0559 9944,2387 18651.4540 98i42*2 000006 ,000070 .419698*02 .67*01 .114642*01
ETHNOL 799.1022 1041,H86 7440.7544 23085.5050 .498567*02 ,999992 ,999927 ,100000*01 .100000*01 .999994*00
WATER .0023 .0028 3*47,4417 20882,1670 ,231020*02 000003 ,000003 ,111699*01 .241059*01 .98364600
TOTAL 799,1602 1041,1773 7747273.7 18448765,0
MOLE FRACyI ON wAyER (ENJRAINER FREE 9ASI8) .000003 ,000003
KTRAY* PRESSURE" 49,720 TE^Pf 234,558 M 2 N 6

COMP VAPOR M/HR LIQ M/HR LIQ BTU/M VAP BTU/M VP/THETA ALPHA GAMMA THETA
.979429+Q2 4 6
PNTAN2 .5i39 99 i,986i 2 l8646,5n8o 000*44 .l9933*02 0 0
.6 47 *01 11 21*01
ETHNOL 797,7091 1039,7254 7421,5674 23082,7760 ,496905*02 :wm; ,999353 ,100000*01 ,100000*01 ,999943-00
WATER .0024 .0030 3639,4535 20680,9200 .230212*02" .000003 .000003 .111717*01 .241138*01 .983646*00
TOTAL 798.2254 1040,2425 7721503,4 18422972,0
MOLE FRACTION WATER (ENTRAINER FREE BASIS) ,000003 ,000003
KTRAY* 3 PRESSURE" 49.580 TE^P 234,%Q2 Ml 2 N 8

COMP VAPOR M/HR LlQ M/HR LQ BTU/M VAP BTU/M Vp/T TA
HE
X ALPHA GAMMA *
PNTAN2 4.6852 4.6854 9783.6962 18634,6530 000*94 .00592 .1202*2*02 .6Q826I*01 ,1459*
ETHNOL 787,8411 1029,8574 7302,448 23076,2360 .493110*02 ,999503 .994085 .100000*01 .100000*01 .999483-00
WAT R
E
.0025 ,0031 3588,4516 20877,9290 .226336*02 .000003 .000003 ,111836*01 ,241516*01 ,983429*00
TOTAL 792,5288 1034.5459 7566325.0 18267766,0

MOLE FRACTION WATER (ENTRAINER FRE5 3ASIS) ,000003 ,000003
KfRAY* 4 PRESSURE 49,440 TEMP 231,260 M 3 N 7

COMP VAPOR M/HR LIQ M/HR LIQ.BTU/M VAP BTU/M Y ALPHA GAMMA THETA
PNTAN2 39 8050 39 8052 8858 3103 18560 83*0- 950046*02 .004529 052418 121590*02 ,602307*01 113705*01
ETHNOL 7195733 961.5896 65lo!6443 23035,3850 .470586*02 ,995468 ,947579 !*01 .100006*01 .995459-00
,000003 ,000003 ,112886*01 .244678*01 .981333*00

AE ,0024 .0030 3241,9305 20859,2591) .217125*02
..
TOTAL 759,3808 1001,3978,, 6613192.3 7314512.0
R T N W A T R ,000003 .000003
E
MOL F * C i E <ENTAIN R F ^ E E ?ASJS)
E
KtRAY 5 PRESSURE 49,300 *1 211.961 Mi 3 7

COMP VAPOR M/HR L I Q M/HR LQ BTU/M VAP BTU/M VP/THETA X ALPHA GAMMA THTA
PNTAN2 268,0904 268,0906 73l8,o396 18059.58^0 ,787405*02 .039750 ,341087 .425051*02 .537254*01 .108614*01
ETHNOL 517,8967 759,9131 5213,8250 22752i8710 .536685*02 ,960247 ,658911 ,100000*01 .100477*01 .971859-00
W TER
A .0020 ,0026 2642,8492 20730,5130 il*I6-U**02 ,000003 ,000003 ,123329*01 ,275187*01 ,969674*00
TOTAL 785,9892 1028,3062 5923958,0 6625276.4
MOLE FRAfeTON WATER (ENTRAINER FÊS SASIS) .000003 ,000004
KtRAY 6 PRESSUSE* 49.160 TEMP- 178,640 M 3 N* "3

COMP VAPOR M/HR L I Q M/HR L Q BTU/M VAP BTU/M VP/THETA ALPHA GAMMA THETA
PNTAN2 656.3955 656,3956 6894,4,59i i7i94.b**0 5l9n*g2 ,26Q7^7 .69 35i
0 63l956*01 .240146*01 .101820*01
ETHNOL 294,4158 036,4321 4862,3906 22244,0940 ,175479*02 ,739211 ,309646 100000*01 ,117350+01 ,947050-00
WATER .0022 .0028 2472,8385 20500,1590 1759T5*i ,000002 .000002 222579*01 ,603523*01 .959809-00
TOTAL 951.8135 1192,*3T5 7133842.3 17835185,0 Computer Output Page 13

MOLE FRACTION WATER (ENTRAINER F"*E5 3ASIS) .000003 ,000007
3
KTRAYs PRESSURE 49,020 TE'1P 1 6 9 . 1 9 4 M 3 N" 3
p
COMP VA OR M/HH LIQ M/HR LIQ BTU/M VAP BTU/M VP/THETA X Y ALPHA GAMMA THETA
PNTAN2 792.9419 792.94?0 6*17,9567 16948,7490 . 4 * 2 0 3 5 * 0 2 .55Q284 .781714 ,292673*01 .144463*01 .100173*01
FTH-NOL 221,4156 463,4319 4799.1707 22095,0280 . 1 4 3 0 1 1 * 0 2 .449714 .218281 ,100000*01 ,166373*01 .944806-00
W AT(:R .0050 .0056 2441,8741 20432.999Q *429*04 .000002 .000005 ,441599*01 ,171431*02 ,959835*00
T0 AL T 1014.3625 1256.37?5 7430346.8 l833659,o
MOLE FRACTION WATER (ENTRAINER F3E" 3ASIS) ,000009 ,000023
2
KTRAYs PRESSURE 46,980 TE^P 167,474 M* 2 7
?
CMP VA 0R M/HR LIT M/HR LIQ BTU/M VAP B T U / M VP/THETA X Y ALPHA CMMA THETA
PNT AM2 924,6641 24,6642 6797,2936 16904,077 ,*7I540*02 .6311-33 ,801762 .236421*04 .131689*01 ,998997-00
ETWNOL 203.8620 445.9783 4782.087 22067,6550 .137553*02 .368863 .98205 ,100000*01 .l9o947*l ,945259*00
WAT^R .0131 .0137 2433.4969 20420.6820 ,588661*01 .000004 .000013 .532861*01 .237755*02 ,960357-00
TOTAL 102*.5392 1270.5562 7737756,5 1.8439207,0
MOLE FRACTION WATER ( E N T R A I M R R F*E5 3A5IS) ,000012 ,000064
KTRAY= 9 PRESSURE 48.740 TE^P 167,009 Mi 2 N" 6

0MP V A P O R M/HR LlQ M/HR L I BTU/M VAP BTU/M VP/THETA X Y ALPHA GAMMA TH|TA
C
PNTAN2 631.2025 31226 6786.5001 l689i,99io .468633^02 .64905* ,8o6o73 .224776*01 .12963*Q1 .998512-00
ETHNOL 199.9386 441.9550 4773.986 22060,2390 136104*02 .350932 ,193894 ,100000*01 ,197856*01 ,945469-09
WATER .0341 ,0347 2429.1187 20417.3430 * 3822*9*01 .oooojii ,000033 .556344*01 .237304*02 .980537-00
TOTAL 1031,1753 1273,9?2 7750579.6 18452055,0
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 ) .000031 .000171
KTRAYs 1 PRESSURE* 4 8 , 6 0 0 TEMP* 166.766 M* 2 N* 6

COMP VAPOR M/HR LIT M/HR LIQ BTU/M VAP BTU/M VP/THETA X Y ALPHA GAMMA THETA

2 332.4716 832.4717 6777.2436 16885,6750 .467014*02 .652849 ,807122 ,222596*01 .128637*01 .998423-00
8
ETHNOL l9R,8485 440 649 4765.5584 22056.36oo .347 4
lg
WATER ,0877 ,' 2425,3626 20415,6010 ! 5*78907*01 .000027 :i & 'Minm $w&
TOT - 103.4078 1273.4248 7743044.8 18444509,0
MOLE FRACTION WATER (ENTRAINER FRE IUSIS) .000078 ,000441

KTRAYs i l PRESSURE* 48,460 TE^P* 16*.557 M* 2 N* k
CONP V P0R M/HR ALIO M/HR LIQ BTU/M V P A BTU/M VP/THETA X Y ALPHA GMMA THETA
PNTAN2 932.5859 32.5860 6767.7421 I6880.257o r+656-13*2 .6537127 80748Q 222373*01 .128557*01 .998403-00
ETHNOL 198,2818 440.2982 4757.7173 22053.0310 .134698*02 .346204 .945640-00
WAT R ,2240 .2246 2421.5060 20414,1040 ,576065*01 ,0000^9 ,960670-00
E
. 1031.09i7 1273.1Q97 7730Q85.3 18431551,0

MOLE FRACTION WATER (ENTRAINER FREE B A S I S ) ,0002p0 ,00112e
KTRAY* 1 2 PRESSURE* 48,320 TEMP* 1 6 6 , 3 4 3 Ma 2 N *
COUP V A P O R M/HR L I Q M/HR L I Q BTU/M VAP BTU/M VP/THETA Y ALPHA GAMMA THfTA
PNTAM2 332,2150 832.2152 6756,8310 16874,6930 ,464180*02 ,653979 8076Q2 .222620*01 .126551*01 ,998385*00
ETWNOL 197,6918 439.7081 4748,7144 22049,6130 ,134043*02 ,345845 ,191845 .100000*01 .199964*01 ,945688*00
WAT R E
.5703 .5708 2417.0756 20412.5660 ,573175*01 ,000176 ,000553 ,565548*01 ,264472*02 .960708*00
TOTAL 1030.4771 1272.4941 77i2565.2 l84i4Q4liO
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 ) ,000510 ,002876
V
8 Ma 2 N 6
KTRAY* 1 3 PRESSURE 48 1 8 0 TE P 166,097
T U / M VP/THETA X Y ALPHA GAMMA THETA
0MPC V A P O R M/HR L I Q M/HR LIQ B V A P gTU/M
A
PNT AN2 3 L 1 0 0 6 31.100* 6742,1831 16868,30?0 462556*TJ2 654003 ,8 7425 .223160+01 .128596*01 .998324-00
0
ETHNOL 196,7734 438,7897 4736.6308 22045,6850 ,133303*02 ,345548 .9168 ,100000*01 ,199956*01 ,945688*00
WATER 1,4478 1.4493 2411.1252 20410,7990 ,5699*0l .000449 ,001407 ,566762*01 .265084*02 .960717*00
TOTAL 1 0 29,3218 1271,3308 7685310.7 18386810.0
A S S > .001296 ,007304
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
E B I
KTRAY* 14 PRESSURE* 48.040 TE^P* 165.766 Ms 2 7

Computer Output Page l A
L I Q M/HR L T Q BTU/M V A P BTU/M VP/THETA X Y ALPHA GAMMA THETA

COMP V A P O R M/HR
2 92.22B8 828,2290 6718,2870 16859,718 ,460426*02 .653721 _ ,998133-00
,806559 ,224263*01 ,128732+01 w
THNOL 194,9825 436,99&8 4716,9242 22040,4060 .132332*02 .345140 ,189881 ,100000*01 199722+01 ,94557000
E
WATER 3.6558 3.65*4 2401.4117 20408.4250 .565557*01 ,001139 ,003360 .568041*01 ,2*5457+02 ,960652*00
TOTAL 1026.8671 1269.8842 763435Q.7 1.8335807.0
MOLE F R A C T I O N WATER ( E N T R A I N E R F R E E BASIS) .003290 ,018404
KTRAY* 1 5 PRESSURE* 47,900 TEMP* 165.227 M* 3 N 3

COMP V A P O R M/HR LlO M / H R LIQ BTU/M VAP BTU/M VP/THETA X Y ALPHA GAMMA THETA
PNTAN2 821.2204 21.2205 6672.9946 16845.7060 .457047*02 ,652722 ,804006 .226759+01 .129094+01 ,997709-00
ETHNOL 191,0846 433.1010 4679.5937 22031.7840 .130792+02 .344396 ,187079 .100000+01 .198941+01 .945163*00
WATER 9.1057 9.1062 2382.9789 20404.5470 ,558635*01 .002882 ,008915 ,569528+01 .265271+02 ,9*0408*00
TOTAL 1021,4107 1263.4277 7528436.8 18229770,0
MOLE FRAC i0N wAyER (ENyRAINER FREE BASIS)
T
,008298 ,045485
NEXT TRAY IS FEED TRAY
8 Ma 3 * 4
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 VAP BTU/M VP/THETA X Y ALPHA GAMMA THETA

2 8 0 51856 8Q5 1857 6581,6141 1.6819 ll8o ,450731+02 .649994 797554 232732*01 ,130017+01 99*623*00
ETHNOL 182'.4605 424,4768 4604.3625 2 2 0 1 5 * . 40*0 ,127925+02 ,342798 ,180731 ,100000*01 .196836+01 .944075*00
WATER 21.9231 21.9?36 2345.7019 20397,1830 ,545688+01 ,007208 ,021715 .571457+01 .2*3*94+02 .959741*00
TOJAL 1009.5691 1251.5862 7305293.0 18006621.0
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 ) ,020593 ,107264

KTRfiY* 1 7 PRESSURE 47,620 TE^P* 162,133 M 3 N* 5
T U / M V A P TU/M VP/THFTA X Y ALPHA GAMMA ^HPTA
0MPC V A P O R M/HR LiQ M/HR LQ B B
PNTAN2 75fi.29 5 75O.29Q0 16765,3520 .438322+Q2 .43332 ,78337 .247i47*oi ,l3229l*oi .994il7*oo
0
0 65o3,8753
ETHNOL 160,0411 60.0374 4540.4524 21982,2030 .122352+02 ,339151 ,167097 ,100000+01 .191758*01 ,941578*00.
WATER 47,4410 6,8606 2313.8971 20382,2610 ,520498+01 .017517 ,049533 ,573936*01 .2387Q9*02 ,93620400
TOT 957.7726 917.89Q 5622309.8 17063895,0
MOLE FRACTION WAT R
E ( N T R A I N R FRE
E E 3ASI8) ,049112 ,228651
KTRAYs PRESSURE ,480 TEMP* 160.367 5
L I Q M/HR L I Q BTU/M VAP BTU/M VP/THETA Y ALPHA GAMMA THETA
COMP VAPOR M/HR ,818033
777,9226 777,9222 6244.8645 16719,4820 ,428265*02 ,811883 .126923+01 .10033+01 ,991243*00

2
130.7335 130.7299 4328,252 21953.7990 .117269*62 ,174487 ,136441 .100000*01 .36598+01 ,943219*00
ETHNOL
WATER 49,5142 8,9337 2207.3051 20369,4990 ,498386*01 ,007460 ,051676 .883494+01 .65858+02 ,959426*00
TOTAL 958.1704 9!7.5858 5443553.7 I6883l4li0
MOLE FRACTION WATER (ENTRAINER FREE BASIS) .041106 ,274701
ACCUMULATOR AND HEATER OR SU3C00LER CALCULATIONS CYCLE NO 1 Computer Output Page 15
ACCUMULATOR
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
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
FRACTION OF AQUEOUS PHASE .059107

TOTAL HFAT ,55574808*07 BTU/HR
CONDENSER HEAT LOAD ,11327660+08 BTU/HR
NO HEATER OR SUBCOOLER
FRACTION OF AQUEOUS PHASE TO SATISFY WATER BALANCE ,956^1*22-00 Computer Output Page 16

ENTRAINER MAKE-UP .40584534-03 M/UR

PRODUCT OUT
COMP PRODUCT M/HR
PNTAN2 .0004
ETHNOL .0037
WATER 40.5805
T0 AL
T
40.5845
Table II. Column Profiles in Azeotropic Distillation
Dehydration of Aqueous Ethanol

Using n-Pentane as Entraner
Fraction Fraction Fraction

Tray No. Pressure, Pentane Water in Vapor Ethanol
(Equil.) t, F psia in Liquid (Pentane-Free) in Liquid
18 160.37 47.48 0.818 0.275 0.175

17 162.13 47.62 0.643 0.229 0.339
16" 164.20 47.76 0.650 0.107 0.343
15 165.23 47.90 0.653 0.045 0.344
14 165.77 48.04 0.654 0.018 0.345
13 166.10 48.18 0.654 0.0073 0.346
12 166.34 48.32 0.654 0.0029 0.346
11 166.56 48.46 0.654 0.0011 0.346
10 166.77 48.60 0.653 0.00044 0.347
9 167.01 48.74 0.649 0.00017 0.351
8 167.47 48.88 0.631 0.000064 0.369
7 169.19 49.02 0.550 0.000023 0.450
6 178.64 49.16 0.261 0.000007 0.739
5 211.96 49.30 0.040 0.000004 0.960
4 231.26 49.44 0.0045 0.000003 0.996
3 234.10 49.58 0.00049 0.000003 0.9995
2 234.56 49.72 0.00005 0.000003 0.99994
1 234.75 49.86 0.000006 0.000003 0.999992
Reboiler 234.91 50.00 0.000001 0.000003 0.999997
B o t t o m Product, M o l e fraction ethanol 0.99999706

M o l e fraction water 0.00000232
M o l e f r a c t i o n pentane = 0.00000062
Stripped Water Product, M o l e fraction water = 0.99999

M o l e fraction ethanol = 0.000009
M o l e f r a c t i o n pentane = 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 from
99.6-45.0 m o l e %. In this same region the pentane 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 ,

B L A C K , GOLDiNG, A N D DITSLER Computer Calculations
160 200 240

TEMPERATURE, F
Figure 1. Temperature profile for 50 psia column dehydration of
aqueous ethanol using n-pentane
n-pentane-to-ethanol ratio 3.22 (mole basis)
20
TOP
FEED 16 ENTRAINER
/WATER IN "IN LIQUID
VAPOR
3 12 (ENTRAIN
ER FREE)
>- ETHANOL
< 8
IN LIQUID
0 . 1 . 1 . 1 1 1 .
0 20 40 60 80 100
MOLE, %
Figure 2. Composition profiles in 50 psia column dehy
dration of aqueous ethanol using n-pentane

100
TRAYS
Figure 3. Relative volatility profiles in 50 psia column dehydration of
aqueous ethanol using n-pentane
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 Calcuhtions 87
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. While
several different entrainers m i g h t b e u s e d to p r o v i d e a separation, the
final 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 . If
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 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 .
8 12 16 20
TRAYS
Figure 4. Effect of changing the n-pentane-to-ethanol ratio (mole

basis) on trays required

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

to-ethanol ratio (mole basis)
DIETHYL ETHER
135 psia
\ BENZENE
1 \ 14.7 psia
" \
PENTANE
50 psia
LZ L 1 , I
0 40 80 120
MOLE FRACTION WATER IN BOTTOM PRODUCT, 10 6
Figure 6. Comparing entrainers, n-pentane, benzene, and diethyl

ether, for water content of ethanol product

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 frac-
t 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 - 6
has b e e n u s e d i n
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. 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

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
1 \ DLETHYL-
\ ETHER
^ 135 psia

-
1 \ BENZENE
1 \ 14.7 psia
!^ 3
\N-PENTANE \
\ 50 psia
L _ I . I . 1
20 40 60
TRAYS, EQUILIBRIUM
Figure 9. Comparing tray requirements for the entrainers, n-pen

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

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 the
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 v
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

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 coefficient
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
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-1-
propanol (2-butanol), and 3-methyl-1-butanol (isoamyl alco-
hol). 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 mix-
tures, water-ethanol-1-propanol, waterethanol-2-methyl-
1-propanol, and water-ethanol-3-methyl-1-butanol. Equi-
librium 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

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 Y
a n d /i L
are e q u a l .
/i = /,
V L
(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 0lj
(3)
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, 8
Pi s
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
phase, a n d /i 0L
are calculated b y procedures described b y Prausnitz
et al. (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 E
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), w h o s h o w that m a n y c o m
m o n expressionse.g., those o f v a n L a a r a n d M a r g u l e s a r e deduced
f r o m t h e g e n e r a l expression of W o h l (3).
C u k o r a n d P r a u s n i t z (4), h o w e v e r , p o i n t o u t that W o h l ' s general
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 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
(1,6,7). W i l s o n s equation and the modification proposed b y Renon and
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 Non-Random

Two-Liquid (NRTL) 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) a n d other w o r k e r s

(6,7), 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.

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 ^ + t ^ ^ K - i ^ M ^ 1
) (5)
2 Gxki k ' = 1
2 Gx kj k I 2 GjcjXk
k-\ k=l \ k=l
where = number of components
(a ~~ 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 par-
t 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 .

T a b l e I. F u g a c i t y Coefficients
Component Temperature, C ,
Water 80 0.9925
90 0.9960
130 1.0150
100 1.0000
Ethanol 80 1.0015
90 1.0119
100 1.0240
1-Propanol 80 0.9898
90 0.9954
100 1.0018
2-Methyl-l-propanol 80 0.9726
90 0.9809
100 0.9904
3-Methyl-l-butanol 80 0.9535
90 0.9608
100 0.9686
130 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
9
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
2
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.
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

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 system, 1-propanol-
water, a n d the heterogeneous 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 and experimental vapor-liquid equi

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

Directly measured, Gadwa (15)
Directly measured, Murti and Van Winkle (12)

Figure 2. Comparison of calculated and experimental vapor-liquid equi

librium data at 760 mm Hg. 2-Methyl-l-Propanol (1)-Water (2).

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 found

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 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 AZEOTROPIC DISTILLATION
Table II. 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 0.050 0.126

101.88 0.080 0.200
101.55 0.085 0.215
101.03 0.090 0.235
98.07 0.155 0.332
94.67 0.220 0.460
94.08 0.243 0.479
90.96 0.330 0.595
89.34 0.382 0.658
87.56 0.465 0.712
86.75 0.490 0.742
86.11 0.510 0.770
85.24 0.560 0.790
84.18 0.610 0.817
83.67 0.635 0.845
82.54 0.705 0.875
81.45 0.770 0.915
81.11 0.800 0.920
80.06 0.870 0.950
Table III. VaporLiquid Equilibrium Data at 760 mm. H g

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

0 5 1
Figure 3. Vapor-liquid equilibrium data at 760 mm Hg. Ethanol (1)-

2-Methyl-l-Propanol (2).
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 = 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 alcohol-water
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 a = 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

0 5 1
Figure 4. Vapor-liquid equilibrium data at 760 mm Hg. 3-Methyl-l-

Butanol (1)-Water ( 2 ) .
Table IV. N R T L Parameters for the Binary Systems

Isobaric Systems at 1 A t m .
( gia-fW ( gai-gu)
Refer- cal./gram cal./gram
ence a mole mole
E t h a n o l U ) - W a t e r (2) 11 0.475 121.0 1161.5

1 - P r o p a n o l ( i ) - W a t e r (2) 15,12 0.500 438.4 1762.9
2 - M e t h y l - l - P r o p a n o l (1)-Water (2) 9 0.475 611.5 2475.7
3 - M e t h y l - l - B u t a n o l U ) - W a t e r (2) 0.300 -386.9 3483.8
E t h a n o l (1 ) - l - P r o p a n o l (2) 16 0.500 465.5 -324.5
Ethanol (i)-3-Methyl-l-
B u t a n o l (2) 16 0.475 20.8 7.4
Ethanol (J)-2-Methyl-l-
P r o p a n o l [2) 0 0

Table V . VaporLiquid Equilibrium Data at 760 mm H g

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

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 91.46
0.3156 0.1996 0.4521 0.2854 88.68 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
0.5562 0.2981 0.4572 0.4474 84.09 85.1
0.1255 0.3990 0.2158 0.5602 87.85 87.76
0.2611 0.3974 0.3274 0.5145 85.24 85.09
0.3722 0.3897 0.3791 0.5041 83.95 83.46
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 0.6009 82.55 82.28
0.4006 0.4991 0.3385 0.6149 81.32 81.10
0.0954 0.6042 0.1347 0.7448 83.97 84.08
0.2124 0.5908 0.2339 0.6877 82.05 81.93
0.4614 0.4118 0.3870 0.5465 82.46 80.23
0.1021 0.6959 0.1266 0.7982 81.94 81.99
0.1952 0.7051 0.1955 0.7680 80.14 80.11
0.0757 0.8162 0.0865 0.8764 80.15 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.

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
0.7248 0.0303 0.8455 0.0589 94.46 93.57
0.2944 0.0263 0.6809 0.0729 104.88 100.44
0.7784 0.0269 0.8464 0.0565 94.56 93.78
0.8878 0.0094 0.8412 0.0277 95.22 95.40
0.0344 0.0241 0.8492 0.0456 95.14 94.13
0.4465 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
0.2774 0.1984 0.4574 0.4082 96.20 92.15
0.2087 0.1867 0.3944 0.4306 99.46 93.92
0.3781 0.3232 0.4331 0.5084 88.31 88.31
0.6071 0.2999 0.4801 0.4971 84.75 86.25
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
0.0312 0.8920 0.0343 0.9551 80.02 80.09
0.0499 0.8998 0.0532 0.9402 79.38 79.45
0.0680 0.8989 0.0706 0.9252 78.96 78.99

Predicted using N R T L equation.
6
Measured.


>
>
<
LOOfCpCBDO
MOLE FRACTION OF WATER IN LIQUID

Figure 5. Comparison of calculated and experimental volatilities of 1-pro-
panol relative to ethanol in presence of water
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) equation proposed b y Renon

a n d P r a u s n i t z (8) 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

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 Oils 109
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 suffi-
c 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, sus-
p 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 .

Azeotropic 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 described
(1,2,3,4,5,6,7), 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 boiling
point. 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 re-
flux 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.

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 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
Table I. Azeotropes of Water and Entrainers
Temperature, Composition % Separated

C (1 atm) by Weight Layers
Boiling
Point Azeo. Azeo. Upper Lower
Compound Temp. Vapors Layers Layers Volume, %
Toluene 110.6 79.8 99.9 0.1 82 Up

Water 100 85 20.2 0.1 99.9 18 Low
m-Xylene 139.1 60 99.95 0.05 63.4 Up

Water 100 94.5 40 0.05 99.95 36.6 Low
n-Octane 125.7 74.5 99.98 0.02 80 Up

Water 100 89.6 25.5 0.02 99.98 20 Low
Butanol 117.7 55.5 77.5 8.0 71.5 Up

Water 100 93 45.5 22.5 92.0 28.5 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 sedi-
m 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 azeo-
t 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

7 A L A S SA A N D O T H M E R Demulsification of Crude Oils 113
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 . A
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 nec-
essary 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 ; other-
w 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 AND AZEOTROPIC DISTILLATION
Laboratory 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 prefer-
able.
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 de-
c 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.

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 . It is w a s h e d w i t h
solvent to free i t of o i l , d r i e d , a n d w e i g h e d . 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, re-
m 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

CONDENSER >
Figure 2. Flow sheet for removing emulsified water by azeo-

tropic 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 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
column. 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 ex-
tractor. 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 per-
m 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 .

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 solvent-
e 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

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

p u b l i c a t i o n s (e.g., 8), 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 scavenger
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 unrecoverable
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 . 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 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 water.
A b r a s i o n i n the expensive centrifuges has b e e n a major operational
charge. 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 coker
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 , which
goes to the refinery. 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 is
suitable, since i t t h e n becomes the a z e o t r o p i c entraner for the water.
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 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

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 en-
trainer, 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 distilla-

tion 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 nota-
tion. The calculation sequence is outlined, and a correction
algorithm based on Newton's method is derived. This re-
quires the calculation of the Jacobian matrix of partial deriv-
atives, and an analytical method for obtaining these deriva-
tives 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 dis-
tillation 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 TiERNEY Nonideal Mixtures 123
a n d p r o v i d e s for a n y interstage flow 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 1) of the phase compositions. T h e t o t a l n u m b e r of
v a r i a b l e s is (2m + 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 balance
equations to g i v e the a d d i t i o n a l equations n e e d e d . 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 investigations Roche (4) has d e m o n s t r a t e d quadratic
convergence for c o m p o s i t i o n d e p e n d e n t l i q u i d extraction problems at
constant temperature. H e essentially iterates o n a l l (2m + 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 Separation System
The 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. T h e matrix notation
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), a n d a l l s y m b o l s are defined b e l o w .

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*) = (1)
3
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 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 + Qf = 0 (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
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
f
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
> 3
- ' 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 T I E R N E Y Nonideal Mixtures 125
H H{X\ X\ . . X", T) (6)
G G(Y ,2
Y,3
. . Y,m
T) (7)
( , X, 2 3
. . X,
m
T) (8)
( F , 7, . . F ,
2
T) (9)
K 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 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
omitting X 1
and Y 1
as arguments i n E q u a t i o n s 6 - 9 .
The Calculation 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

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 m
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 3 W
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 . 1 2 m
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 .
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 ) v + 1 - (C)v} = - (D)v (11)
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 3 m
E k
= AY k k
- ***; 1 < k < m (12)
= BL H + AVG + Q+ Q f (13)
T h e most r a p i d convergence 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, A N D T B E R N E Y Nonideal Mixtures 127
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. F i r s t , h o w e v e r , i t is
p a r t i t i o n e d into (m + l ) 2
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 ' ' * - 1 ( 1 4 )
J* = { ~ ; 2 < k <m (15)
f^;k = m+l (16)
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,
% = - B _ 1
A = - R (17)
Because X . . X 2 m
are iteration variables,
I l ; 2 < j, k < m
jk (18)
where 8 jk = 0 if /^ 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

t h e fact that X 1
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 (19)
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 liquid compo-

sitions.
AY*
yû= ~ Y-'S -1 2
<h k <m (20)
L = v-iR-i L; 2 < k < m (21)

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 that the
differentiation is w i t h respect to X , k
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 m
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, and
n o w L is a vector. 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. T h e d e r i v a t i v e of E q u a t i o n 3
by V gives,
dV =Y -1
{R - 1
S - Y} ;
7 ?
< j <
(22)
P a r t i a l derivatives of the p h y s i c a l properties 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 example,
( 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 2
holding
Y ... Y
3 m
and constant. A l l vector derivatives 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
+ Y1
dX k
" ~ dXk
(23)
K'X'
- - dX"

8. B R U N O , YANOsiK, A N D TiERNEY Nonideal Mixtures 129
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<j,k<m
2. F o r / = 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 1
Y^R-'L + P K 1
-
(24)
K 1
^ 1
^ ) ; 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 l -1
(|^) (y" ) 1
( R X S - Y )
_ 1 p
(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 B i ^ i f i + i |,(|)(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 v f (J^j Y" 1
(E X E-1 p
- 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 m+1
~dX r

T h e n , u s i n g E q u a t i o n 20, a n d after some rearrangement.
W = B L (J^ - A (Jf^j R - L (30)
2 < 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 , = BL(g) Av(g) + (32)
Change of Iteration 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 fixed.
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 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 Nonideal Mixtures 131
Initial Values for Iteration 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 2
... X , T ) .
m
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 m
Modification of Correction Algorithm
The requirement 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 . We
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 flows
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 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 ex-
c 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 one-
h 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.

Application 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 . An extractive
distillation problem from Oliver (6) 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 (7).
Table I. Norms for Successive Iterations of Sample Problem
Iteration Composition, Energy Balance,

1 2.9 2.8E4
2 1.6 1.6E4
3 1.5 7.2E4
4 1.4 3.2E4
5 1.2 9.8E3
6 5.8E-1 7.5E3
7 7.8E-2 1.5E3
8 1.7E-3 8.1
9 5.0E-6 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 m y
(
2\ 2
9 = (e )
i3 ) (33)
V = i y=i /
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. For
e a c h r u n the values of v and u n 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 TiERNEY Nonideal Mixtures 133
<7u i t e r a t i o n variables. 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 be-
cause 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 de-
crease 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. Two of
the r u n s d i d not converge.
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 range
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 proposed
Table II. Results for Different Vapor Flows and Starting

Conditions for Sample Problems
Condenser Reboiler Number of
Temp Vapor Flow Temp. Vapor Flow Iterations to
hi Vu h Vl Converge
210 .5 270 1.5 9a
270 .8 330 1.5 10

210 .8 275 1.0 17
210 .1 275 1.5 Diverge
220 .4 300 1.0 10
210 .4 275 1.0 Diverge
0
This is run reported in Table I.

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 method
(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 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 p u b l i s h e d solutions for nonideal
distillation problems. 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 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
u
l e a v i n g stage / w h i c h goes to stage i

C 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 ,... 2
X ,T) m
D T h e d i r e c t s u m of t h e error vectors, ( E , . . 1
E ) m+1
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 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
G 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
H 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

8. B R U N O , YANOSIK, A N D T I E R N E Y Nonideal Mixtures 135
I T h e identity matrix
J 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 ,
2
e a c h of size b y n. ] kj 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 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
m 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
Q 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

Q f 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
t i
per unit time

R D e f i n e d as B A ; R A B
_ 1 1 _ 1
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
t
U A vector e a c h element of w h i c h is 1.0

V 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
X 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
Y 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
Sjcj 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
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 Liquid-
Liquid 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 sys-
tem primarily shows small negative deviations of the coeffi-
cients 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 been
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), Herington (3), and
136

9. BURKHEAD AND SCHRODT Acetic Acid-Acetone System 137
M a r e k (4). H e r e w e t r y to o b t a i n x-y-t 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, L
= 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)
and
k = (3)
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
K
= - W
T) m 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 m + e =
d 1, w i l l a l l o w E q u a t i o n
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 - 1 , .
and
V 1 +4/c - 1 0
(6)
2k

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 TQ m (n\
Y- = p e (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
Tm2 = P)m2 ,2 (8)

m32 m
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 Omko V 1 + 4Ko?o2 ~ 1 / x 0
i m = 7 = = = * W
YmAo V 1 + 4k 0 - 1
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 are

given by
yt = 7 2
+ 2 < ; 2
(10)
and
m2 + 2e d 2 /-,-,
^2 = jr u t ;
1 + <*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 ,
V 1 + 4UL y 2 (2-2/ ) 2 ~ 1 /iox

" 2 = 2/2
2jfp y i (2-y0 ( 1 2 )
and
V 1 + 4k x ( 2 - x ) - 2 2 1 , 1 Q N

- 2 =
* 2
2k x, ( 2 - x ) 2
( 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 Z 2
and 2 results:
2/ =
2 2 2 2 2 2 2 (14)

9. B U R K H E A D A N D SCHRODT Acetic Acid-Acetone System 139
where
z = 1 + V 1 + 4K 0 P 2
1 + V 1 + 4 t f 2/ (2-2/ ) 2 2
and
= i + V T + . = ( 1 6 )
1 + V 1 + 4ifc z 2 (2-z ) 2
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
* = r r V ( 1 7 )
and
xi = T-r (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:
1 + *K P(2-2/ ) - V 1 + AK y (2-y ) 2 2
2K P(2-y y
2
= yi (19)
2
and
1 + 4fc(2-s ) - 2 V 1 + 4fc s 2 (2- ) 2 . .

= X i ( 2 0 )
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 2 2
(2-y ) (1 + V 1 + 4K y , ( 2 - y , ) )
2

and
2 (l-x 2 + V 1 + 4fc x {2-x ))

2 2
(23)
(2-x ) 2 (1 + V 1 + 4fc ( 2 - ) )
2 2
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 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 Ah /R
M
values a n d E q u a t i o n 24 w i l l test f o r consistency.

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 .
_Air
Condenser Leak
Drying Tube
Ice-Water
Bath
Surge Bottles
rtr 1
Manostat
Variac
Transformer
Vacuum Absolute
Liquid Phase Water Pump Mercury
Manometer Manometer
Sampling Flasks
-Vapor Phase Sampling Flask
Figure 1. Schematic diagram of experimental apparatus
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 A N DA Z E O T R O P I C DISTILLATION
120 r 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1
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). T h e s e y's are p r e s e n t e d
0 0.1 0.2 0.3 0.4 0.5 0.6 0.7 0.8 0.9 1.0
Mole Fraction Acetone in Liquid phase
Figure 3. Activity coefficients of acetic acid-acetone at 760 mm Hg

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 2
0.25 j 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1
0 0.1 0.2 0.3 0.4 0.5 0.6 0.7 0.8 0.9 1.0
Mole Fraction Acetone in Liquid Phase
Figure 4. 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 0) = 10.4205 - (26)
a n d e x p e r i m e n t a l values o f K 0 (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

temperature a n d pressure. Differences b e t w e e n t h e values of log
Ko(pô) a n d 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)

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 # ( 7 6 0 ) = 9.9905 + 0.00224* - % 2 ( >

28
and
- l o g # 5oo) = 10.0505 + 0.00209* -

( % g (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 2 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 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 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

0.20 r 1
_0 inL 1 1 1 1 1 1

1 1 1 1 1 1 1 1 1 1 1 1 L 1
0 0.1 0.2 0.3 0.4 0.5 0.6 0.7 0.8 0.9 1.0
Figure 6. 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 x 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 2
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
j In ( , tt/Tx ) dx h

Table I. Modified Redlich-Kister Consistency Test Results
1 @ = 0
P ,mmHg
T I In ^ dxi / l ^ d T Area
J O l
m J T @ X 1 = 1 H 1
760 -0.0234 -0.0465 0.0231

500 - 0.0244 - 0.0492 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 2
M
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 Symbols
D H e r i n g t o n test p a r a m e t e r
Ak 31
heat o f m i x i n g
J 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
k 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
R gas constant
absolute t e m p e r a t u r e
t 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
y 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
c 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

Superscripts
L l i q u i d phase
V 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 deter-
mined 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 indi-
cate 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 re-
quires use of three ordinary distillation columns and extrac-
tive 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, re-
c 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 acti-
v 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 Mixtures 149
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 for
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 mixture obtained
f r o m a d s o r b e r regeneration. Previous binary 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 (2, 3) i n d i c a t e d t w o b i n a r y azeotropes (water-THF and water-
M E K ) a n d a t w o phase region ( w a t e r - M E K ) . 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 Vacuum Pump
2 Manometer
3 Mtrcury Traps
4 Jacket Condenser
5 Sample Condenser
Thermocouples
7 Thermistors
8 Jacket Heater
9 Reboiler
I Jacket
II Contactor Body
12 Contactor Throat
13 Contactor Sample
Valve
14 Vapor Sample
Volve
15 Needle Valves
16 Nitrogen Tank
Figure 1. Schematic diagram of the equilibrium still

T a b l e I. Liquid Phase
Run ywater. , YTHF. XMEK,
No. mole fr. mole fr. mole fr. mole fr. mole fr.
1 .288 .181 .532 .561 .166
3 .217 .289 .494 .486 .237
4 .256 .177 .566 .866 .039
5 .257 .209 .534 .506 .181
6 .275 .388 .337 .377 .399
7 .236 .223 .541 .460 .211
8 .199 .102 .699 .322 .124
9- .226 .178 .596 .697 .092
10 .297 .478 .225 .375 .486
11 .244 .216 .540 .508 .194
12 .226 .058 .717 .585 .046
13 .234 .162 .604 .869 .037
14 .267 .327 .407 .379 .342
15 .314 .299 .387 .507 .267
16 .250 .182 .568 .507 .169
17 .247 .174 .580 .438 .181
18 .121 .039 .841 .071 .062
19 .103 .278 .619 .043 .409
20 .230 .619 .152 .110 .787
21 .163 .123 .714 .118 .197
22 .248 .477 .275 .184 .607
23 .311 .599 .090 .281 .665
24 .269 .291 .440 .438 .287
25 .244 .304 .452 .289 .374
26 .215 .040 .746 .296 .051
27 .181 .350 .474 .501 .279
28 .206 .284 .510 .169 .409
29" .262 .284 .453 .594 .208
.862 .064
30 .165 .436 .399 .093 .587
31 .201 .149 .650 .189 .213
32 .095 .523 .383 .034 .678
33 .219 .006 .775 .596 .005
34 .134 .000 .866 .091 .000
35 .153 .000 .847 .121 .000
36 .221 .000 .779 .424 .000
37 .211 .000 .790 .661 .000
38 .160 .018 .822 .131 .029
39 .141 .031 .828 .093 .048
40 .144 .059 .796 .113 .092
41* .293 .366 .342 .502 .315
.892 .064
42 .353 .370 .277 .469 .383
.914 .058
43 .197 .071 .732 .177 .103
44" .318 .447 .235 .518 .368
.862 .101
a
Two-phase run.

10. LYBARGER AND GREENE Separation of Mixtures
Activity Coefficients
XTHF y water fMEK y THF Temp.

mole fr. C.
.273 2.021 1.722 1.946 64.7

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

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.
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 mer-
cury. 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 waterMEK
(66.2 mole % M E K , normal boiling point 73.4C) and water-THF

10. L Y B A R G E R A N D G R E E N E Separation of Mixtures 153
Water KEY
0.00 0.10 0.20 0.30 0.40 0.50 0.60 0.70 0.80 030 100
THF 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

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 O60 0.70 030 0.90 1.00
THF 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 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

and Ellis (6) 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 :

D cd = (x ic + x) id (log y id - log y ) ic (2)
i=l

10. L Y B A R G E R A N D G R E E N E Separation of Mioctures 155
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 2 2 + a3 X 3 + a X i +4
2
a&2
2
+ (3)
aaXz2
+ 7&2 + a&ix z + a& x 2 z
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
l9 2 s
ketone, a n d t e t r a h y d r o f u r a n , respectively.
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 a
en a5
W a t e r (1)
( R = 0.996) 2.2301 -4.5041 2.4778
MEK (2)
( R = 0.983) -0.0426 2.0063 - 0.1641
THF (3)
( R = 0.997) -0.0017 2.0828 0.1995
a
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 .

THF
WATER
f~~

IV
20 Plates
Feed 5 th 15 Plates 15 Plats
Feed 5 th Feed * 1
L/D 9
L/D* 3 L/D3
WATER MEK
Figure 4. Schematic diagram of solvent separation scheme
T e r n a r y Separation B y Distillation. 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

10. LYBARGER AND GREENE Separation of Mixtures 157
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 separa-
t 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. The
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 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. Column Specifications
Stream No. 1 2 3 4 5 6 7 8 9 10
Flow Rate
(moles/hr) 100 20.0 80.0 34.3 26.8 7.5 21.6 15.2 5.2 10.0
Composition
(mole fraction)
THF .075 .374 .635 .799 .016 .999
MEK .075 .369 .002 .215 .011 .984
H0 2 .850 .258 .998 .150 .190 .660 .999 .001
DMF .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

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 (2)
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 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

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
2
where the
t o t a l pressure is g i v e n b y :
n c = x p ' m + (-)' , 2 (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 temperature
dependence 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. T h e two-constant
form gives:
m - -W-AM-*)) + (i-x) { - ^ - T^fb)} <*>
in y, - - H i - * , - - j,^} (2b)
W h e n t h e best values o f A i a n d A 2 1 2 have been found, the vapor compo

s i t i o n is c a l c u l a t e d :
ln(l-y) = ((1-)' /) - 2 ( -V )(II-p' )/RT -

2 2 2 2 ln(l-A x)
12
_ j(l-x) A12 _ xA 21 ) <>

3
X
\ 1-A x 12 1-A 21 (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 F U R T E R Prediction of Vapor Composition 161
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

point. T h i s r a t i o , c, 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 molar
v o l u m e s of the t w o l i q u i d s ( 5 ) 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 y fit G*/RT-x fit

(y-y) (y-yc)
.034 .495 93.8 .000 .003
.074 .595 87.2 -.012 -.007
.124 .646 84.2 -.007 .000
.170 .674 82.5 -.005 .004
.284 .696 81.7 -.001 .009
.446 .720 80.8 -.003 .005
.633 .752 79.4 -.019 -.016
.759 .807 78.5 -.012 -.014
.858 .869 77.7 -.006 -.011
.938 .936 77.9 .001 -.003
Sample deviation .0098 .0098
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) ln{\-A x)l2 (4)
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. A
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 . T h e values of
a n d /

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. G r a p h i c a l smoothing
of the o b s e r v e d - 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

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 E
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 are s m a l l . This
c o n c l u s i o n is not u n e x p e c t e d . However, if the following equation
In y = / ) - (Bu-VOffl-p'O/RT - ln(l-A {l-x))

2l
ttl-x)A l2 xA 21 ) <>
5
+ U X )
\ l-A x
12 l-A (l-x)f
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. T h i s effect i s n o t
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 below.
Table II. Comparison of the T - * Fit and the G^/RT-x Fit Using
the Wilson Equation
Salt y <sG RT
E
Reference

4.88 .0079 6.45 .0082 8
6.24 .0068 4.48 .0064 12
9.69 .0045 6.34 .0059 18
NH CI 4 13.66 .0098 5.84 .0098 U
tNaCl 18.82 .0119 11.79 .0054 14
t NaBr 27.42 .0471 60.27 .0375 15
t NaN0 3 30.06 .0260 31.75 .0187 u
tKCl 31.40 .0301 28.74 .0200 U
KBr 28.09 .0109 10.72 .0150 15
KI 19.48 .0234 14.08 .0098 15
K S02 4 3.95 .0118 6.23 .0082 U
Ca(N0 ) 3 2 33.69 .0078 28.12 .0096 11
Ba(N0 ) 3 2 20.20 .0152 15.45 .0130 u
CuCl 10.31 .0092 7.54 .0096
HgCl 2 5.10 .0138 3.55 .0119
HgBr 2 8.40 .0273 17.47 .0261
Hgl 2 13.69 .0142 13.98 .0146 u
LiCl" 6.07 .0062 12.54 .0056 16
t NaCl 20.96 .0184 14.64 .0143 17
t Na S0 2 4
6 23.95 .0264 19.63 .0132 18
tKCl 22.90 .0180 10.14 .0088 17
" 3.65 .0058 4.00 .0045 16
BaCl 2
d
11.42 .0110 4.34 .0085 U
KN0 3
e 4.94 .0099 7.70 .0078 19
(NH ) S(V 4 2
24.9 .0358 35.3 .0320 14
a
Data of limited range: x = 0.3-1.0.
6
Data of limited range: x = 0-0.8.
c
Data of limited range: x = 0.2-1.0.
d
Data of limited range: x = 0-0.6.
Partially miscible systems-use of three constant Wilson equation,
e
t See text.


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 variable
m e t r i c a l g o r i t h m s (10). 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. T o free the p r o g r a m f r o m this constraint,
A i w a s r e p l a c e d b y 1-A
2
2
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 = 2 1, a n d analysis s h o w e d that this w a s the
lowest p o i n t of the A i - A i 2 2 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

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 (22)
2 LAYERS H
.1 .2 .3 .4 .5 .6 .7 .8 .9
X
Figure 2. Comparison of the experimentally de

termined vapor compositions for the ethanol-water-
saturated potassium nitrate system (19) with the
three constant Wilson T - x fit
Observed
Calculated

.1 .2 .3 .4 .5 .6 .7 .8 .9
X
Figure 3. Comparison of experimentally deter
mined vapor compositions for the ethanol-water-
saturated 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 2 and
12
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. 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

Table III. Constants for the Fit Using the Wilson Equation
Salt m const. A M A I 2 C Refere

.8140 .1325 8
.7899 .1813 12
' .8526 .0848 13
NH4CI .9294 -.0032 1.013 .8829 .4154 U
NaCl .9935 .1109 1.019 .9476 .3692 14
NaBr .9174 .0776 0.912 .9138 .5005 15
NaN0 3 .8853 -.0704 1.020 .9420 .5592 14
KC1 .9547 -.0037 1.000 .9198 .4314 14
KBr .9572 .0360 0.983 .9214 .2744 15
KI .9383 .0719 0.886 .8433 .4000 15
K S0
2 4 .9962 .0105 1.023 .9188 .0802 U
Ca(NO,) 2
1.0712 .9368 0.747 .8531 .0090 11
Ba(N0 ) 3 2 1 0 1.027 .8208 .1780 11
CuCl 1 0 1.042 .8486 .0565 14
HgCl 2 1 0 .892 .8314 .0791 14
HgBr 2 1 0 .965 .8428 .1263 14
Hgl 2 1 0 1.010 .8267 .1095 14
LiCl .9659 .9199 .492 .7926 .5457 16
NaCl .9935 .1109 1.019 .9332 .3308 17
Na S0 2 4 1.019 .0969 1.000 .9349 .1633 18
KC1 .9640 .0235 1.000 .9307 .3226 17
KI .9383 .0719 .975 .9275 .3285 16
BaCl 2 .9906 .0348 1 .9170 .2142 11
KN0 3 .8570 -.2250 1.000 .7515 - . 3 9 0 8 2.959 19
(NH ) S0 4 2 4 .9731 .0487 1.011 .9409 .0449 1.250 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 v a p o r pressures b e i n g so adjusted. For
example, 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 tested, t h e y have
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 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.

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 E
= 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
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.

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., Butter-
worth, 1969.
21. Redlich, O., Kister, A. T., Ind. Eng. Chem. (1948) 40, 345.
22. Newton, ., Intern. Symp. Distillation, Inst. Chem. Engrs. (London), Sec-
tion 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 Azeotropic (Continued)
distillation
Acetone 43
azeotrope, methanol 47
-methanol separation 48 ternary wo, *
system acetic a c i d - 136 ADP/ADPLLE 65
Acid, Lewis 50 results compared for dehydrat
ing aqueous ethanol,
Activity coefficients 17,124,140
calculated 65
dilution 49
or extractive distillation
liquid phase 2,3,150,151
paraffin 20 columns 93
selectivity and 27

ADP
-ADPLLE 91 Barker's method 159
simplified calculations by Base, Lewis * 50
subprogram 68 Basic flow 114
A D P P L L E , subprogram 69 Basis
Agent, separating 37 cost calculation 25
Air pollution 148 design 23
Alcohols, mixtures of water and Batch azeotropic distillation 115
simple 93 Benzene 65, 89
and diethyl ether, comparison
Algorithm, modification of
for the entrainers, n-pentane 87
correction 131
Binary system 99
Alternate solvent recovery 32
Boiling point 107
Analysis
economic 24 Bonding solvents, hydrogen 21
regression 155 Bottom product 12
venture 24 1,3-Butadiene recovery 33
Applications 43 Butanol HI
Aqueous
ethanol C
calculated azeotropic distilla
tion results compared for Calcium chloride 39
dehydrating 65 Calculated azeotropic distillation
dehydrating 14 results compared for dehydrat
mixtures, dehydration of . . . . 2 ing aqueous ethanol 65
systems 41 Calculation
Aromatics 58 basis, cost 25
Association computer 64
complexes 17, 42 design 91
factors, vapor, and liquid 138 distillation 122
Automated feature, use of the . . . . 69 for the extractive distillation of
Azeotrope 38,110 aqueous ethanol mixtures . . 4
methanol-acetone 47 sequence 125
of water and entrainers 112 by subprogram A D P , simplified . 68
Azeotropic tray-to-tray 70
column 115 Changing the molecular environ
distillation 14,65 ment 1
batch 115 Chemistry of the salt effect 40
column 12 Choice of an entraner 87
comparison of extractive with 12 C3 hydrocarbon mixtures 34
modified 115 C4 hydrocarbon separations 33
171

Circulation rate 17 Dehydrating

solvent 24 aqueous ethanol 14
Clay, colloidal 120 calculated azeotropic distilla-
Coefficient tion results 65
activity 17,124,140 process, demulsifying 114
dilution activity 49 Dehydration of aqueous ethanol
distribution 64 mixtures 1,118
fugacity 97 Demulsification of crude oils 108
imperfection-pressure 2 Demulsifying, dehydrating process 114
liquid phase activity 3,150,151 Density, polar cohesive 51
paraffin activity 20 Design
selectivity and activity 27 basis 16,23
Cohesive calculations 91
density, polar 51 process 16,106
energy, polar 48 of separation processes 2
Coke 119,120 Diethyl ether 65,89
Colloidal clay 120 comparison for the entrainers,
Column 35 n-penane, benzene, and
azeotropic 115 diethyl ether 87
distillation 12 Digital computers 2
or extractive distillation 93 Dilution
efficiency 24 activity coefficients 48
extractive distillation 6 relative volatilities through
profiles 84 G L C , infinite 59
solvent recovery 10,11 Dipole-induced dipole 49
Comparison Dispersion 49
for the entrainers, n-pentane, Dissolution, feed 117
benzene, and diethyl ether 87
Dissolved salt 37
of extractive with azeotropic
distillation 12 Distillation
Complexes, association 17, 42 of aqueous ethanol mixtures,
Components, feed 1,17, 22, 40 calculations for the 4
azeotropic 14, 65
Composition 7, 35, 94,125,146
liquid 107 batch azeotropic 115
calculations 122
vapor 41,159
column
phase 97
Computer azeotropic 12,13, 93
extractive 6,13,93
calculations 64
methods, multicomponent 157 continuous 115
Concentration costs, extractive 30
extractive 1,12,14,16,148
molal salt 40
saturation 39 modified azeotropic 115
solvent 19 program
A D P / A D P L L E , azeotropic . . 65
Condenser temperature 131
Consistency test 146 ternary azeotropic 68, 72
Content, water 110,114 results compared for dehydrat-
ing aqueous ethanol, calcu-
Cooler, solvent 17
lated azeotropic 65
Correction
algorithm, modification of 131 solvents
matrix, Jacobian 126 ethylene glycol as the extrac-
Cost tive 2
calculation, basis 25 extractive 58
extractive distillation 30 screening of extractive 46
utility 26 using dissolved salts as separating
Cracking 119 agents, extractive 40
Criteria, solvent selection 18 Distribution coefficients 64
D
Dalton's law 152 Ease of separation 40, 46
Data, isobaric vapor-liquid Effect
equilibrium 96,124,136 chemistry of the salt 35, 40
Debye, electrostatic theory of . . . . 42 magnitude of salt 41
Dcantation 114 mixed solvents 52

INDEX
173
Effect (Continued) Extractive distillation (Continued)

of solvent and solute concentra- solvent
tion 50 screening of 46
Efficiency, column 24 using dissolved salts as separating
Electrolytes, solution theory of . . . 40 agents 40
Electrostatic theory of Debye . . . . 42
Energy, Gibbs free 95 F
Energy
molar free 163 Factor, separation 17, 59
polar cohesive 49 Factors, vapor and liquid associa-
Enthalpies for liquid and vapor . . 4,124 tions 138
Entraner 12,64,65,110 Feed 5
azeotropes of water and 112 components 17, 22, 40
choice of 87 dissolution 117
n-pentane, benzene, and diethyl Feedstock 113
ether, comparison for the . . 87 Flow
solvent 116 basic 114
Entrainment 37 vapor 129
Environment, changing the Flowsheet 18,111,157
molecular 1 Foaming 114
Equation Fraction, naphtha Ill
Gibbs-Duhem 155 Fractionation, reverse 28
modified van Laar 3, 66 Free energy 95,161
non-random, two liquid 93 molar 163
nonlinear 122 Fugacity coefficients 94,97
NRTL
Redlich-Kister 164 G
van Laar 132
G C O S process 118
vapor pressure 3
Gibbs-Duhem equation . . . 146,155,159
Wilson 95,160
Gibbs energy 42,95
Equilibria GLC
data 124 infinite dilution relative vola-
isobaric vapor-liquid 93,136 tilities through 59
prediction of three-phase 65, 66 screening solvents through . . . . 58
relative volatilities for three Great Canadian Oil Sands, Ltd.
phase 67 ( G C O S ) Process 118
relation, modified 139
salt effect on vapor-liquid 40
separation system 123 H
stage requirements 28
Heat
three-phase 67 loads 14
vapor-liquid 35, 67,148 recovery system 30
Ethanol 13,39, 86, 89,93 Hydration 43
calculated azeotropic distillation Hydrocarbon 55,93,109
results compared for de-
C 4
hydrating aqueous 65
3
mixtures 48
calculations for the extractive separations, C4 33
distillation of aqueous 4
Hydrogen bonding solvents 21
mixtures
Hypothetical saturation vapor
dehydration of aqueous 1,2
pressure 138
recovery of 7
-water 38,41,97,160
Ethylene glycol 1, 2,12 I
-water 41 Imperfection-pressure coefficients . 2
Extraction, primary 119 Infinite dilution relative volatilities
Extractive distil- through G L C 59
lation 1,12,14,16,132,148
Internal pressure 42
of aqueous ethanol mixtures,
calculations for the 4 Isobaric vapor-liquid
columns, azeotropic or 6, 93 equilibrium data 93,136
costs 30 systems 159
solvent 58 Isothermal-isobaric system 155
ethylene glycol as the 2 Iteration variables 125,127

J Mixture (Continued)
the Scheibel Method, non-
Jacobian correction matrix 126,128 hydrocarbon 47
Modification
of correction algorithm 131
process 29
values 9
Modified
Kerosene 117
azeotropic distillation 115
Knockback section, solvent 37, 44
equilibrium relation 139
Redlich-Kister test 140
L van Laar equations 3, 66
Molal salt concentration 40
Law, Raoult's 18,101
Layer, top bitumen 121 Molar free energy 163
Lewis Molecular environment, changing
acid 50 the 1
base 50 Multicomponent systems 13,17,157
and Matheson technique 70
Limit, miscibility 22
Liquid Naptha fraction HI
associations factors, vapor and . 138 Newton's methods 122,134
composition 107 Non-hydrocarbon mixtures: the
equation, non-random, two . . . . 93 Scheibel Method 47
equilibrium data, isobaric Nonideal mixtures 122
vapor- 35,93,136,148 Nonideality 1,95
-liquid tieline 153 Nonlinear equations 122
phase Non-random, two-liquid equation . 93
activity coefficients . . . 2,3,150,151 Notation, matrix 122
miscibility 107 N R T L equation 96
systems, isobaric vapor- 159
and vapor, enthalpies for 4
phases, relative distributions
between the separable . . 2 Octane HI
Loading, solvent 24 Oil
Lowest water content 89 wet sludge 115
demulsification of crude 108
M Olefins 58
Operating temperature 24
Matrix, Jacobian correction . . . . 122,126 Optimum design 16
Matheson technique, Lewis and . . 70 Othmer recirculation still 43
Mercuric chloride 41
Methanol
-acetone azeotrope 47
separation, acetone- 48 Parachor method 56
Method Paraffin
Marquardt's 134 activity coefficient 20
non-hydrocarbon mixtures: The -olefin system 19
Schiebel 47 n-Pentane 1,12,65,89
Parachor 56 benzene and diethyl ether,
Weimer-Prausnitz ( W P ) 57 comparison for the entrainers 87
multicomponent computer 157 Petroleum crudes 108
Newton 134
P P, 47
3-Methyl-l-butanol-water 100 t
Methyl ethyl ketone, water- 148 Polar

Miscibility cohesive
limit 22 density 51
liquid-phase 107 energy 49
solvent 20
Mixed solvents effect 52
Pollution, air 148
Mixture
THF-MEK 149 Potassium acetate 37
C3 hydrocarbon 34, 48 Prediction of three-phase equilibria 66
nonideal 122 Pressure 94,107
ternary 96 coefficients, imperfection- 2
of water and simple alcohols . . . 93 equations, vapor 3

INDEX 175
Pressure (Continued) Screening

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

System (Continued) Utility costs 26

isobaric vapor-liquid 159 phase 2
multicomponent 17,93 composition 97
paraffin-olefin 19
ternary 103
van der Waal forces 42
van Laar equation 95,132
Temperature . . . .7, 54, 94,110,125,161 Vapor
denser 131 composition 41,159
operating 24 enthalpies for liquid and 4
reboiler 131 flows 129
Ternary relative distributions between
azeotropic distillation program . 69 the separable liquid and 2
mixtures 96 -liquid equilibria 35,67,148
separation by distillation 156 and liquid associations factors . . 138
system 103 pressure 110
Test equations 3
consistency 146 hypothetical saturation 138
modified Redlich Kister 140 Variable, iteration 127
Tetrahydrofuran 148 Vector differentiation 126
Theory Venture analysis 24
of Debye, electrostatic 42 Viscosity 108
of electrolytes, solution 40 V L E data 96
T H F - M E K mixture 149 Volatilities 17, 40,47, 89,104,145
Three-phase equilibria 66 through G L C , infinite dilution
relative volatilities for 67 relative 59
Top bitumen layer 120 profiles 7
Top product 5,12, 86 solvent 22
Transport 119
Tray-to-tray 70,71 W
Trays, stripping 11 Water
Two content 11,110,114
liquid equation, non-random . . . 93 lowest 89
phase runs 153 and entrainers, azeotropes 112
ethanol- 38,41,160
U ethylene glycol- 41
methyl ethyl ketone 148
Undissociated salt molecules 41 and simple alcohols, mixtures of 93
U N I V A C 1108 computer 4 Weimer-Prausnitz ( W P ) method . 56
Use of the automated feature 69 Wilson equation 95,160


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Extractive and Azeotropic

In Extractive and Azeotropic Distillation; Tassios, D.;

Based on papers presented at

two symposia sponsored by the

Division of Industrial and

of the American Chemical Society

at the 160th Meeting, Chicago,

Ill., Sept. 17, 1970, and the

163rd Meeting, Boston, Mass.,

April 14, 1972.

ADVANCES IN CHEMISTRY SERIES 115

AMERICAN CHEMICAL SOCIETY

In Extractive and Azeotropic Distillation; Tassios, D.;

American Chemical Society

All Rights Reserved

Library of Congress Catalog Card 72-92811

PRINTED IN THE UNITED STATES OF AMERICA

In Extractive and Azeotropic Distillation; Tassios, D.;

In Extractive and Azeotropic Distillation; Tassios, D.;

In Extractive and Azeotropic Distillation; Tassios, D.;

1 Dehydration of Aqueous Ethanol Mixtures by Extractive Distillation

2 Process Design Considerations for Extractive Distillation: Separation of Propylene-

3 Extractive Distillation by Salt Effect

4 Rapid Screening of Extractive Distillation Solvents: Predictive and Experimental

5 Azeotropic Distillation Results from Automatic Computer Calculations

6 Prediction of Isobaric Vapor-Liquid Equilibrium Data for Mixtures of Water

7 Demulsification of Crude Oils: Use of Azeotropic Distillation

8 Distillation Calculations with Nonideal Mixtures

9 Isobaric Vapor-Liquid Equilibrium in the Acetic Acid-Acetone System

10 Separation of Water, Methyl Ethyl Ketone, and Tetrahydrofuran Mixtures

11 Prediction of Vapor Composition in Isobaric Vapor-Liquid Systems Containing

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

In Extractive and Azeotropic Distillation; Tassios, D.;

Newark College of Engineering

In Extractive and Azeotropic Distillation; Tassios, D.;

In Extractive and Azeotropic Distillation; Tassios, D.;

Dehydration of Aqueous Ethanol Mixtures

C. BLACK and D. E. DITSLER

Although nonidealities in vapor and liquid phases complicate

In Extractive and Azeotropic Distillation; Tassios, D.;

Table I. Constants for Calculating Imperfection-Pressure Coefficients

Ethanol 516.3 63.1 0.089 4.75 75.9

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

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 three

In Extractive and Azeotropic Distillation; Tassios, D.;

Table II. Constants for Vapor Pressure Equations 0

Ethanol 8.16280 1623.22 228.98

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 -

w h e r e t h e differential heat of m i x i n g (Li) x is g i v e n as

(L). = 2.303#( l o g < ) . / ( 1 / ) (3)

Table III. Modified van Laar Coefficients for the System

Binary % Ai, A c t,C

Ethanol-ethylene glycol 0.276000 0.259279 0.000000 75.0

In Extractive and Azeotropic Distillation; Tassios, D.;

Table IV. Enthalpies for Liquid and Vapor

Ethanol 32 0.00 19800.0

Ethylene glycol 100 3637.0 30724.0

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

In Extractive and Azeotropic Distillation; Tassios, D.;

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

In Extractive and Azeotropic Distillation; Tassios, D.;

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

Table V . Extractive Distillation Column