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and
B.D. Crittenden
12 Januaty
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
azeotrope;
thermal
swing; zeolites
and experimental
method
1988
Vol 2 June
77
An experimental
Nitrogen
experiments
were analysed
and/or Karl Fischer titration.
lb
To ccn8,er
Schematic
diagram
of the experimental
apparatus
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)
MTZ L
Tnl,, (s)
(cm)
(C)
0.128
0.125
0.106
2580
2280
1380
134.5
146
172
105
105
115
0.04
0.03
0.10
0.121
0.120
0.112
3660
1680
1680
105
105
104
0.03
0.09
0.16
0.120
0.123
0.145
92
106
136
106
107
110
106
108
109
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
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
P
gas chromatography
or Karl Fischer
titration
by
8 Purification 1988
Vol 2 June
26.1 1
An experimental
Table 2
Sieve
N2 flow
(cm3 min-
RTP)
Pressure
(bara)
Initial
loading
(g/g)
3A
4A
I.0
0.089
0.128
0.125
0.128
0.122
0.08
1 .o
0.67
0.54
0.121
0.145
0.112
0.128
0.163
0.129
0.163
0.146
0.122
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)
Gas Separation
79
An experimental
4000
Time (5)
6000
8000
6000
8000
I
4000
Time (sl
OO
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
80
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
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
KJ---
I
0005
I
005
I
001
01
Figure 6
sieve; -,
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
Vol 2 June
81
An experimental
<
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
82
Gas Separation
& Purification
1988
Vol 2 June
1
2
3
increasing
increasing
decreasing
and
An experimental
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
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,
ChemicalEngineers,
Gas Separation
& Purification
1988
Vol 2 June
83