1

Dehydration of Aqueous Ethanol Mixtures

by Extractive Distillation

C. BLACK and D. E. DITSLER

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Shell Development Co., Emeryville, Calif. 94608

Publication Date: August 1, 1974 | doi: 10.1021/ba-1972-0115.ch001

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 -

In Extractive and Azeotropic Distillation; Tassios, D.;

Advances in Chemistry; American Chemical Society: Washington, DC, 1974.
 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
β
Α11 δα 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

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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
Publication Date: August 1, 1974 | doi: 10.1021/ba-1972-0115.ch001

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, γ/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*Pi°fl,° 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 Ρ*°, 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

In Extractive and Azeotropic Distillation; Tassios, D.;

Advances in Chemistry; American Chemical Society: Washington, DC, 1974.
 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 Ρ = A - BIT - C log Τ ; P, mm Hg, T , °K.
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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
Publication Date: August 1, 1974 | doi: 10.1021/ba-1972-0115.ch001

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 δ*, 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^^^iU), (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#(Δ l o g γ < ) . / Δ ( 1 / Τ ) (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-ethylene glycol 0.251000 0.23579 0.000000 87.8
Ethanol-water 0.74600 0.40080 0.000000 87.8
E t h y l e n e glycol—water 0.00142 0.00081 0.000000 87.8
Ethanol-ethylene glycol 0.23000 0.21607 0.000000 100.0
Ethanol-water 0.76050 0.39250 0.000000 100.0
Ethylene glycol-water 0.00130 0.000714 0.000000 100.0

In Extractive and Azeotropic Distillation; Tassios, D.;

Advances in Chemistry; American Chemical Society: Washington, DC, 1974.
 4 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 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
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300 11600.0 35193.0

400 15889.0 37700.0
Water 100 1225.0 19916.0
Publication Date: August 1, 1974 | doi: 10.1021/ba-1972-0115.ch001

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)

Ο 150
ζ
< y 75%
χ
ι—
LU
Ζ 100 h-
eg •

LU ^^77.78%
50
- i
— — — — 80%
: 1 r ι , 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

In Extractive and Azeotropic Distillation; Tassios, D.;

Advances in Chemistry; American Chemical Society: Washington, DC, 1974.
 1. B L A C K A N D DITSLER Dehydration of Ethanol Mixtures 5
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Publication Date: August 1, 1974 | doi: 10.1021/ba-1972-0115.ch001

2 3 4 5
ETHYLENE GLYCOL/ΕΤΗANOL (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-θ +
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 104.0°F. 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 173°F, 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

In Extractive and Azeotropic Distillation; Tassios, D.;

Advances in Chemistry; American Chemical Society: Washington, DC, 1974.
 6 E X T R A C T I V E A N D A Z E O T R O P I C DISTILLATION

24

REBOILER
20

16
CONDENSER
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12
Publication Date: August 1, 1974 | doi: 10.1021/ba-1972-0115.ch001

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 110°F on tray 22, liquid solvent at 173°F on tray 43.

In Extractive and Azeotropic Distillation; Tassios, D.;

Advances in Chemistry; American Chemical Society: Washington, DC, 1974.
 1. B L A C K A N D DITSLER Dehydration of Ethanol Mixtures 7

Table VI. Extractive Distillation Column

Ethanol-Ethylene G l y c o l - W a t e r

Temperature, Composition, and Volatility Profiles

Ethanol in Water in
Vapor, Mole Liquid, Mole Ρ 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
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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
Publication Date: August 1, 1974 | doi: 10.1021/ba-1972-0115.ch001

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.

In Extractive and Azeotropic Distillation; Tassios, D.;

Advances in Chemistry; American Chemical Society: Washington, DC, 1974.
 8 E X T R A C T I V E A N D A Z E O T R O P I C DISTILLATION
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Publication Date: August 1, 1974 | doi: 10.1021/ba-1972-0115.ch001

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/Ε = 4.08688, R/F = 1.5537 moles, 99.99% recovery, ethanol

In Extractive and Azeotropic Distillation; Tassios, D.;

Advances in Chemistry; American Chemical Society: Washington, DC, 1974.
 1. B L A C K A N D DITSLER Dehydration of Ethanol Mixtures 9

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 Κ 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
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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.
Publication Date: August 1, 1974 | doi: 10.1021/ba-1972-0115.ch001

MOLE FRACTION
Figure 6. Composition profiles in the extractive distillation of
aqueous ethanol with ethylene glycol
EG/Ε = 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

In Extractive and Azeotropic Distillation; Tassios, D.;

Advances in Chemistry; American Chemical Society: Washington, DC, 1974.
 10 E X T R A C T I V E A N D A Z E O T R O P I C DISTILLATION

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
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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
Publication Date: August 1, 1974 | doi: 10.1021/ba-1972-0115.ch001

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

Ethanol-Ethylene G l y c o l - W a t e r

Temperature and Composition Profiles

Water in Ethylene Glycol

Vapor, Mole in Liquid, Ρ 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.

In Extractive and Azeotropic Distillation; Tassios, D.;

Advances in Chemistry; American Chemical Society: Washington, DC, 1974.
 1. B L A C K A N D DITSLER Dehydration of Ethanol Mixtures 11
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Publication Date: August 1, 1974 | doi: 10.1021/ba-1972-0115.ch001

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 .

In Extractive and Azeotropic Distillation; Tassios, D.;

Advances in Chemistry; American Chemical Society: Washington, DC, 1974.
 12 E X T R A C T I V E A N D A Z E O T R O P I C DISTILLATION

I f t h e t o p p r o d u c t ( w a t e r ) f r o m t h e solvent r e c o v e r y c o l u m n is to
be discarded, the two distillation columns w o u l d be operated to reduce
e t h a n o l a n d e t h y l e n e g l y c o l to l o w c o n c e n t r a t i o n s , as i l l u s t r a t e d i n the
c a l c u l a t i o n s s h o w n here. H o w e v e r , w h e r e the o v e r a l l p l a n t s c h e m e is
s u c h t h a t t h e w a t e r p r o d u c t m i g h t b e r e c y c l e d a n d used—e.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
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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 .
Publication Date: August 1, 1974 | doi: 10.1021/ba-1972-0115.ch001

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 entraîner 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 10τ 1

MOLE FRACTION
Figure 8. Composition profiles for solvent recovery column

Stripping water from aqueous ethylene glycol

In Extractive and Azeotropic Distillation; Tassios, D.;

Advances in Chemistry; American Chemical Society: Washington, DC, 1974.
 1. B L A C K A N D DITSLER Dehydration of Ethanol Mixtures 13

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 Entraîner = 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 .
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S o l v e n t o n t r a y 43 Entraîner 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 β
Publication Date: August 1, 1974 | doi: 10.1021/ba-1972-0115.ch001

T o p l o a d = 13.12 m i l l i o n
Btu/hour
T o w e r d i a m e t e r = 5.3 feet
Ethanol product:
W a t e r 16 p p m (mole basis)
S o l v e n t 1.2 p p m (mole basis)
E t h a n o l recovery f r o m feed =
99.99%
C o n d e n s e r l o a d — 11.33 m i l l i o n
Btu/hour
T o w e r d i a m e t e r < 5 feet
Ethanol product:
W a t e r < 3 p p m ( m o l e basis)
n - P e n t a n e < 1 p p m (mole basis)
E t h a n o l r e c o v e r y f r o m feed
>99.99%

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 α

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.

In Extractive and Azeotropic Distillation; Tassios, D.;

Advances in Chemistry; American Chemical Society: Washington, DC, 1974.
 14 E X T R A C T I V E A N D A Z E O T R O P I C DISTILLATION

I f n-pentane is selected as the entraîner 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
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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
Publication Date: August 1, 1974 | doi: 10.1021/ba-1972-0115.ch001

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 χ
(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 χ
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 /
αν 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 /
γι 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 /
Οι 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 /

In Extractive and Azeotropic Distillation; Tassios, D.;

Advances in Chemistry; American Chemical Society: Washington, DC, 1974.
 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. Α., 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.
8. Hoffman, E. S., "Azeotropic and Extractive Distillation," Wiley, New York,
Downloaded by GRAND VALLEY STATE UNIV on November 14, 2013 | http://pubs.acs.org

1964.
9. Gerster, J. Α., Chem. Eng. Progr. (1969) 65 (9), 43.
10. Black, C., Golding, R. Α., Ditsler, D. E., Advan. Chem. Ser. (1972) 115, 64.
RECEIVED November 24, 1970.
Publication Date: August 1, 1974 | doi: 10.1021/ba-1972-0115.ch001

In Extractive and Azeotropic Distillation; Tassios, D.;

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