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An experimental comparison of type A

molecular sieves for drying the


ethanol-water azeotrope
B. Sowerby

and

B.D. Crittenden

School of Chemical Engineering,


Received

12 Januaty

University of Bath, Bath BA2 7AY, UK

1988

The recovery by adsorption of ethanol from aqueous vapours of composition around that of the
azeotrope has been studied using fixed beds packed with various type A molecular sieves. For similar
adsorption and desorption conditions, 4A is superior to 3A molecular sieve giving higher capacities,
shorter mass transfer zone lengths and greater rates of desorption. Very low water concentrations
(< 0.05 wt% water) can be achieved provided that the initial bed temperature and initial water
concentration in the feed are not too high. Type 5A and 1 OA molecular sieves are not suitable for this
separation since high temperature increases which arise from the adsorption of both water and ethanol
cause the ethanol to react to form undesirable by-products.
Keywords:

adsorption;

molecular

sieves; ethanol-water

In the industrial production of ethanol, whether by


chemical or biochemical process routes, the raw product
is generally a dilute aqueous solution. The recovery of
ethanol to a dryness in excess of the azeotropic composition
(95.6wt% ethanol at 78.2C, 1.013 bar) is normally
achieved by azeotropic or extractive distillation processes.
However, such separation processes are energy intensive.
Douglas and Feinberg have made a comparative study of
other separation methods and have concluded that a
selective adsorption process would be a simple and
economical alternative.
Teo and Ruthven confirmed experimentally that fuelgrade ethanol (99.19 wt%) could be produced by liquid
phase adsorption of water from aqueous ethanol using 3A
molecular sieves. The rate of adsorption was shown to be
controlled primarily by intraparticle pore diffusion
resistance with some additional contribution from external
film resistance. Garg and Yon3 proposed that the heat of
adsorption could be stored in the bed of molecular sieve to
be used subsequently in the desorption stage. The
economic advantages of such an adsorptive heat recovery
process were demonstrated for drying a mixture of near
azeotropic composition to motor-fuel grade ethanol.
Recently, Carton et al? experimentally compared
drying the ethanol-water azeotrope by vapour phase and
liquid phase adsorption of the water onto 3A molecular
sieve. They concluded that the vapour phase process was
more favourable since steeper breakthrough curves and
thus greater adsorptive capacities were obtained. They
also indicated that an additional disadvantage of liquid
phase adsorption is the retention of a substantial amount
0950-42 14/88/020077-07$03.00
(9 1988 Butterworth Et Co (Publishers) Ltd.

azeotrope;

thermal

swing; zeolites

of feed in the void volume at the end of the adsorption


stage.
The present study was initiated in order to determine
the relative merits of various type A molecular sieves for
the recovery of dry ethanol (> 99.95 wt%) from a vapour
feed of composition around that of the azeotrope.
Particular attention is paid to the balance between the
maintenance of a product with a low water content during
the adsorption step, i.e. high selectivity, and the ease of
regeneration by heating, nitrogen purging and pressure
reduction.
Apparatus

and experimental

method

The apparatus, shown schematically in Figure I, consisted


of a 0.0176 m ID stainless steel adsorption column
mounted vertically in a temperature controlled oven. The
column was packed to a height of 40 cm with commercially
available beads of molecular sieve (1.6-2.5 mm diameter,
3A, 44, 5A and lOA, manufactured by the Davison
Chemical Division of W.R. Grace and Company). A
10 cm long bed of glass beads was placed at each end of
the bed of molecular sieve to ensure good flow distribution.
Seven thermocouples, protruding through the column
wall into the bed of molecular sieve, were used to monitor
the temperature variations during both adsorption and
desorption.
A constant vapour feed flowrate (in the range 0.0330.098 cm3 s- of original liquid) of known composition (in
the range 3.75-13.5 wt% water) was provided by a positive
displacement metering pump and a single tube evaporator.

Gas Separation Et Purification

1988

Vol 2 June

77

An experimental

comparison of molecular sieves: B. Sowerby and B.D. Crittenden

Nitrogen

experiments
were analysed
and/or Karl Fischer titration.

lb

To ccn8,er

Schematic

diagram

of the experimental

apparatus

Adsorption experiments were carried out with flow in the


upwards direction with the initial column temperature in
the range 88-136C.
For desorption
the column
was heated to a final
temperature
between 161 and 265C purged with a
regulated supply of hot nitrogen (60-500 cm3 min- RTP),
and in some experiments evacuated to a pressure between
0.5 and 1.Obara. The flow for desorption was downwards.
Prior to the next adsorption
experiment
the bed of
molecular sieve was completely regenerated by heating to
310C for 24 h in a stream of nitrogen. Upon condensation
the products
of both the adsorption
and desorption

Table 1

Experimental conditions

Initial bed
effluent
(wt% H,C)

Initial bed
temp (C)

4A

Feed flow
(cm3 liquid s-l)

Av. bed
load
(g/g)

Time for T,,,,

MTZ L

Tnl,, (s)

(cm)

(C)

Variation in initial bed temperature


0.092
3.95
0.02
0.098
3.89
0.03
0.098
5.21
0.12

0.128
0.125
0.106

2580
2280
1380

134.5
146
172

105
105
115

Variation in feed flowrate


0.06 1
3.75
0.088
4.85
0.098
4.60

0.04
0.03
0.10

0.121
0.120
0.112

3660
1680
1680

105
105
104

Variation in feed concentration


0.088
4.85
0.090
9.17
0.085
12.8

0.03
0.09
0.16

0.120
0.123
0.145

92
106
136

Variation in initial bed temperature


0.096
4.40
0.02
0.096
4.80
0.03
0.085
4.40
0.09

106
107
110

Variation in feed flowrate


0.033
4.38
0.065
5.61
0.095
4.71

106
108
109

Variation in feed concentration


0.096
4.80
0.085
9.55
0.087
13.50

99180
57165
63150

1263
823
1090

137
153
162

40.48
27.66
(43.67)

85395
69090
63480

790
904
1015

1680
810
780

153
163
178

27.66
79.79
(123.11)

69090
71790
86760

904
911
1156

0.163
0.148
0.087

2820
2580
1800

138.5
149
159

28.72
26.1 1
(47.39)

89820
80520
42960

927
935
791

0.03
0.04
0.10

0.122
0.148
0.114

6480
3000
1800

135
147.5
144

34.81
32.92
(42.51)

73095
70395
53925

355
550
810

0.03
0.08
0.12

0.148
0.136
0.171

2580
1140
900

149
171
187

80520

935
803
587

3.93
3.93

0.02
0.13

10A

90
109

0.055
0.075

5.0
4.6

3.25
0.50

) Signifies that the mass transfer zone length exceeds the bed length (40 cm)

Separation

kJ given to
effluent ethanol
per kg water
absorbed

39.82
38.07
*( 70.83)

0.093
0.09 1

Gas

Area under
temp. profile
(C)

88
108
123

91
109

78

During
an adsorption
experiment
the temperature
variation through the column and the effluent composition
were monitored until complete breakthrough
of water had
occurred. Example results are shown in Figure 2. Breakthrough was assumed to have occurred when the effluent
contained 0.05 wt% water. Table I shows that under certain
conditions both 3A and 4A molecular sieves were capable

Feed
(wt% H,O)

5A

*(

Adsorption

Adsorption experimental conditions and results

Sieve

3A

chromatography

The experimental
conditions
used for a selection of
typical
adsorption
and desorption
experiments
are
summarized
in Tables I and 2, respectively.
To simplify the interpretation
of the experimental
results, it is necessary to minimize
radial temperature
gradients, channelling
and wall effects. However, conflicting criteria arise when attempting to minimize all these
effects simultaneously.
Carbe&
suggested a tube to
particle diameter ratio of less than 5-6 to avoid excessive
radial temperature
gradients, whereas Rase6 suggested
that the ratio should be greater than - 10 to avoid
channelling
and wall effects. As a compromise,
the
experimental
tube to particle diameter ratio in this study
was selected to be in the range 7-l 1.

Alcohol-water

Figure 1

gas

Results and discussion

P
gas chromatography
or Karl Fischer
titration

by

8 Purification 1988

Vol 2 June

26.1 1

An experimental

Table 2

comparison of molecular sieves: B. Sowerby and B.D. Crittenden

Desorption experimental conditions


Final bed
temp (C)

Sieve

N2 flow
(cm3 min-

RTP)

Pressure
(bara)

Initial
loading
(g/g)

3A

4A

I.0

Variation in final bed temperature


245
500
1 .o
230
500
1 .o
161
500
1 .o

0.089
0.128
0.125

Variation in nitrogen purge flowrate


225
500
1 .o
225
100
1 .o
225
60
1 .o

0.128
0.122
0.08

Variation in column pressure


165
200
135
200
135
200

1 .o
0.67
0.54

0.121
0.145
0.112

Variation in final bed temperature


265
500
1 .o
229
500
1 .o
201
500
1 .o

0.128
0.163
0.129

Variation in nitrogen purge flowrate


229
500
1 .o
235
100
1.0
235
60
1 .o

0.163
0.146
0.122

Variation in column pressure


201
500
210
200
208
200

0.129
0.148
0.136

Time (s)

A::8
0.51

Time k)

Figure 3
Effect of the variation in initial bed temperature on the
breakthrough curve. (a) 3A sieve: 0, 123C; A, 108X,
0, 88C.
(b) 4A sieve: l, 136C; A, 106C; 0, 92C

0'
0

1000

2000

3000

4000

I
3000

4000

Time (s)

110

1000

2000
Time (s)

Figure 2
(a) Typical experimental
breakthrough curve and
(b) temperature profile for 4A molecular sieve (feed = 0.096 cm3
liq s-, 4.22 wt% H,O, 120C)

of producing dry alcohol. After breakthrough had occurred


the end bed temperature dramatically increased as the
heat associated with the adsorption of water was released.
The peak temperature and the time at which this event
occurred are given in Table I.
Acetaldehyde and diethyl ether were detected in the
product during the experiments with the column packed
with either 5A or 1OAmolecular sieve. It is believed that
these two sieves adsorbed not only the water but also some
of the ethanol, the chemical present in the greatest
quantity in the vapour feed. The consequential rise in bed
temperature was much more dramatic than with either 3A
or 4A molecular sieves, and peak temperatures of up to
21OC were observed. At relatively high temperatures
molecular sieves are active catalysts for the dehydration of
ethanol and therefore 5A and 10A molecular sieves were
not considered further.
Figures 3-5 show the effects of varying the initial bed
temperature, feed flowrate and feed concentration on the
breakthrough curves with the column packed with either
3A or 4A molecular sieve.
Dry alcohol was only produced if the initial bed
temperature was somewhat less than 123 and 136C for
3A and 4A molecular sieves respectively. Figure 3 shows
that, for conditions when dry alcohol is produced, i.e. the
mass transfer zone (MTZ) length is less than the bed
length, increasing the initial bed temperature decreases

Gas Separation

Et Purification 1988 Vol 2 June

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An experimental

comparison of molecular sieves: 6. Sowerby and B.D. Crittenden

4000
Time (5)

6000

8000

6000

8000

I
4000
Time (sl

OO

the MTZ velocity is proportional


to the fluid velocity, then
for design purposes it could be inferred that the MTZ
length is proportional
to the fluid velocity raised to a
power of about 0.7 for adsorption of water onto 3A and 4A
molecular sieves. Clearly, much more experimental
data
are required in order to establish a more precise relationship for the dependence of MTZ length on fluid velocity.
Figure 5 shows that increasing the water concentration
in the feed decreases the time for breakthrough
to occur,
this event occurring immediately with feed water concentrations in excess of 12-13 wt%. Again the main reason for
earlier breakthrough
times with increasing water concentration is that the adsorbent is exposed to more adsorbate
per unit time.
In general the results given in Figures 3-6 and Table 1
show that for broadly comparable
operating conditions
the performance of 4A molecular sieve, with respect to the
adsorption of water from an ethanol-water
vapour feed, is
superior to that of 3A molecular sieve. The criterion for
this conclusion
is to produce dry ethanol with a short
MTZlength
and a high bed capacity. For 4A molecular
sieve, a maximum capacity of 0.163 g water/g molecular
sieve was experimentally
obtained for the runs in which
dry ethanol was produced (with an initial bed temperature
of 92C a 0.096 cm3 liquid s- feed flowrate containing
4.4 wt% water). The highest capacity with 3A was only

Figure 4
Effect of the variation in feed flowrate on the breakthrough curve a) 3A sieve: l ,0.098 cm3 s-l; A, 0.088 cm3 s-l;
0,
0.081 cm s-l.
(b) 4A sieve: l , 0.095 cm3s-;
A,
0.065 cm3 s-l; 0, 0.033 cm3 s-l

.4

the time for breakthrough


to occur. There are two reasons
for this. First, the capacity of the molecular sieve for water
decreases with increasing
temperature*.
Experimental
capacities were computed from the breakthrough
curve
data and are shown in Table I. Second, increasing the bed
temperature
causes an increase in the rate of diffusion
within the solid, thereby resulting in an increase in the
adsorption rate. Figure 3 and Table 1 also show that for the
runs in which dry ethanol is produced
the time for
complete breakthrough
to occur, and the MTZ length are
reduced as the temperature
is increased.
Figure 4 shows that increasing
the feed flowrate also
decreases the time for breakthrough
to occur. The main
reason is that the adsorbent is exposed to more adsorbate
per unit time, and so becomes saturated more quickly. A
secondary effect, shown in Table 1, is the reduction in
MTZ length as the flowrate is increased for the runs in
which dry ethanol is produced. This observation indicates
that the rate of adsorption
is influenced
by a fluid-side
mass transfer resistance. MTZ lengths are plotted against
MTZ velocities in Figure 6, and show similar trends to
those given by SchweitzeP, who reported that the MTZ
length is proportional
to the MTZ velocity raised to the
power 0.72. The MTZ velocity is plotted against the fluid
velocity in Figure 7. The limited experimental
data exhibit
significant scatter. Nevertheless if it can be presumed that

80

Gas Separation 8 Purification 1988

Vol 2 June

1000

2000

3000

4000

3000

4000

Time(s)
I .o

-.

0.8

s
.5
5
E
8
B
$
.z
w

0.6

0.4

0.2

2000

Time (s)
Figure 5
Effect of the variation in feed concentration on the
breakthrough curve. (a) 3A sieve: 0, 12.8 wt% H,O; A, 9.17 w-t%
H,O; 0, 4.85wt%
H,O. (b) 4A sieve: 0, 13.5 wt% H,O; A,
9.55 wt% H,O; 0, 4.8 wt% H,O

An experimental

comparison of molecular sieves: B. Sowerby and B.D. Crittenden


0.025

200
t

% 002
E
0

g 0.015

00
.

f
L

6
h

60-

F
E 0.01

OQCE

.O

20

I
50

I
40

30

Fluid velocity (cm s-)

KJ---

I
0005

I
005

I
001

01

MT2 velocity (cm s-1

Figure 6
sieve; -,

MTZ length versus MT2 velocity: 0, 3A sieve; 0, 4A


trend given by SchweitzeS (MTZ L cc V$$

0.128 g water/g molecular


sieve (with an initial bed
temperature
of 88C a 0.092 cm3 liquid s- feed flowrate
containing
3.95 w-t% water).
The greater capacity for water of 4A molecular sieve
implies that the larger pore size of 4A enables the water to

MTZ velocity versus fluid velocity (feed concentration


Figure 7
3.75-5.61
wt% H,O, initial bed temperature 88-136C).
0,
3A sieve; 6, 4A sieve

be more easily adsorbed. Two experimental


observations
have confirmed
this. First, Table 1 shows that, for
comparable experimental
conditions, the MTZ length for
3A and thus the resistance for the adsorption of water, is
greater than that for 4A molecular sieve. Second, Table 1
also shows that the amount of heat (approximated
by
integrating
the area under the bed outlet temperature-

ia
I-

,-

Ib

l-

I-

)-

)O
Time (~1

Time(s)

Figure 8
Effect of the variation in the final bed temperature on the extent of desorption. (a), (b) 3A sieve: 0, 245C (126C); A, 230C
(90C); 0,161 C (103C). (c), (d) 4A sieve: 0,265C
(12 1 C); A, 229C (93C); 0,201 C (125C). Temperatures given in parentheses are
the initial bed temperatures

Gas Separation Et Purification 1988

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An experimental

comparison of molecular sieves: B. Sowerby and B.D. Crittenden

<
1000

Time(s)

2000
3000
Time (s)

4000

5000

Figure 9
Effect of the variation in nitrogen purge flowrate on the extent of desorption. (a), (b) 3A sieve; (c), (d) 4A sieve. 0, 500 cm3 min-
N,; a, 100 cm3 min- N,; 0, 60 cm3 min- N2

time curve) carried away by the flowing ethanol per


kilogram of water adsorbed, which is directly proportional
to the heat of adsorption, is in general greater for 3A than
4A molecular
sieve, for comparable
experimental
conditions.
Hence, the heat of adsorption
and so the
forces to be overcome prior to adsorption occurring, are
greater for the adsorption
of water onto 3A molecular
sieve than onto 4A molecular sieve.
Desorption
Desorption
experiments
were performed
immediately
following an adsorption
experiment.
Thus the oven set
point temperature would be increased, nitrogen would be
passed through the column, and, if required, a vacuum
would be applied to the product line. Experimental
conditions
are given in Table 2.
During desorption bed temperatures,
product weights
and concentrations
were monitored. In practice the oven
attained its set-point temperature
within 10 min and the
heat input from the oven ensured that there was no
variation
in temperature
along the column
at any
particular time. The percentage of water removed and the
actual weight of water removed were chosen as the two
parameters
to be used for comparing
the extent of
desorption under varying conditions. Figures 8-10 show
the effects of final column temperature,
nitrogen purge
rate and column
pressure.
With both 3A and 4A
molecular sieves the extent of desorption is increased by:

82

Gas Separation

& Purification

1988

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1
2
3

increasing
increasing
decreasing

the final bed temperature;


the nitrogen purge flowrate;
the operating pressure.

and

These three actions all involve an increase in the amount


of energy to be supplied to the process and thus an
increase in the water removal rate is to be expected.
Figure 8 shows the effect of final column temperature
on the extent of desorption
for 3A and 4A molecular
sieves. The percentage water removed is, for all experimental
conditions
studied, greater for 3A than 4A
molecular
sieve. However, the initial loadings are, in
general, greater for 4A than 3A molecular
sieve, and
Figure 8 shows that the rate of water removal (g s-) is
greater for 4A than for 3A molecular sieve under similar
desorption conditions.
Figure 9 shows the effect of the nitrogen purge flowrate
on the extent of desorption. Comparing the rate of water
removal (again because of the large variation in the initial
loadings), there is little difference in the performance
of
the two sieves.
It is shown in Figure 10 that decreasing the pressure
during desorption results in an increase in the amount of
water removed for both 3A and 4A molecular sieves. No
direct comparison
can be made between 3A and 4A
molecular sieves in this instance as the experiments were
performed at different final bed temperatures, 135-165C
and 200-210C
for 3A and 4A molecular
sieves
respectively.

An experimental

comparison of molecular sieves: B. Sowerby and B.D. Crittenden

c
b
I-

I-

)-

IL
0

2000
Time

3000
(s)

2000

Figure 10
Effect of the variation in pressure on the extent of desorption. (a), (b) 3A sieve: 0,l
sieve: 0, 1 .O bara; A, 0.68 bara; 0, 0.5 1 bara

Conclusions
The recovery of dry ethanol in the vapour phase from an
aqueous ethanol feed using 3A or 4A molecular
sieve
adsorbents has been confirmed experimentally.
Both 5A
and 10A molecular
sieves were found to dehydrate the
ethanol during adsorption and so cannot be used for this
particular drying application.
For similar operating conditions, the capacity for water
of 4A molecular sieve was found to be greater than that of
3A molecular sieve. A longer MTZ length and a larger
amount of heat released during adsorption confirmed that
3A molecular
sieve presents a greater resistance to the
uptake of water than 4A molecular sieve. Consequently
the amount of water which had to be desorbed, under
similar conditions, was found to be greater for 4A than for
3A molecular sieve.
Comparison
of the experimental
results for desorption
indicates that, for similar operating conditions, the rate of
removal of water from 4A is slightly greater than that from
3A molecular sieve. This again infers that 3A molecular
sieve presents a greater resistance to the movement
of
water than 4A molecular sieve.
For equivalent
duties, an adsorption
column packed
with 4A molecular sieve would be smaller and would also

require
packed

Time(s)

3000

.O bara; A, 0.65 bara; 0.0.54

bara. (c), (d) 4A

a reduced energy input when compared


with 3A molecular sieve.

to one

Acknowledgement
The authors wish to acknowledge the award of an SERC
CASE Studentship
to B. Sowerby.

References
Douglas,

L. and Feinberg,

D. Evaluation of non-distillation
Solar Energy Research Institute,
New York SERI/TR-231-1887, (1983)
Teo, W.K. and Ruthven, D.M. Znd. Eng. Chem. Process Des. Dev.
(1986) 25 (1) 17-21
Garg, D.R. and Yon, C.M. Chem. Eng. Prog. (1986) 82 (2) 54-60
Carton, A., Gonzalez, G., Iniguez de la Terre, A. and
Cabezas, J.L. J. Chem. Tech. Biotechnol. (1987) 39 125-132
Carberry, J.J. Chemical and Catalytic Reaction Engineering,
McGraw-Hill, New York, (1976) pp 530-535
Rase, H.F. Chemical Reactor Design for Process Plants, Vol I:
Principles and Techniques, Wiley and Sons Inc., New York (1977)
pp 400 and 537
Yue, P.L. and Birk, R.H. Chem. Eng. Res. Des. (1985) 63
ethanol-separation

processes,

250-258

Schweitzer,

P.A. Handbook of Separation Techniques for


McGraw-Hill, New York, (1979) pp 3.21-3.38

ChemicalEngineers,

Gas Separation

& Purification

1988

Vol 2 June

83