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Liquid-Liquid Extraction
W. A. CHANTRY', R. L. VON BERG,
AND
H. F. WIEGANDT
Extraction efficiencies in conventional countercurrent columns are often poor. Many designs
have been proposed to aid mass transfer by means of agitation. A promising method is that
of pulsating the liquid in a column to provide turbulence throughout the column. The results of
a detailed study of pulsation in both packed and sieve-plate columns are given. As great as
threefold improvement was achieved over conventional operation for the packed column. Efficient performance can be maintained at low feed rates b y pulse action. Only slight reduction
in flooding rate was noted. Sieve-plate construction allowed greater capacity but suspended
material easily plugged the plates. Sieve plates must have small holes, and the column will not
operate without pulsating. Existing packed columns can readily be modified and can be operated conventionally when not pulsated. Emulsion formation may be a problem with some systems
01
N
W
June 1955
Apparatus
The experimental apparatus was arranged as shown in Figure 1.
The two columns interchangeable with the auxiliary equipment
were each constructed from a 4-foot section of 40-millimeter
borosilicate glass tubing. The packed column contained a 27inch section with dumped 1/4-inch porcelain Raschig rings.
The rings were 1/4 x 1/4 inch with a '/rz-inch wall. The packing
after settling had a dry void fraction of approximately 58%.
The sieve-plate column contained 11 plates spaced 3 inches apart
and held in place by a central spacer and support rod. Two sets
1153
Run
No.
R
Ketone
Acid
af
Ex- fi- CU. Ft./Hrfeed
0.2
0.2
0.2
0.2
0.1
0.1
0.1
0.1
0.1
0.1
0.3
0.1
a
feed
19.5
19.5
19.0
19.0
18.9
18.9
19.0
19.0
19.0
19.0
18.8
18.5
tract
15.0
14.7
10.7
12.0
10.7
14.2
13.8
11.8
11.8
13.0
10.7
12.4
nate
12.2
9.1
3.1
4.6
3.4
12.2
9,4
4.7
5.1
6.9
4.2
5.8
4.33
6.08
11.52
9.70
11.82
4.16
6.41
9.98
8.75
8.57
7.87
9.55
Sq. Ft.
7.68
7.86
7.91
7.68
7.26
7.70
8.20
9.32
6.43
9.06
5.81
8.68
Material
Pulse
Balance
DisAccuracy
placeMeasured
Cycles/ ment,
Wt. Out/
minute mm,b Calcd. Wt. I n
6
0.999
54
54
6
0.997
6
54
0.996
6
54
0.996
29
6
1.000
29
6
0.997
29
6
o.gg9
6
29
0.994
47
5
1 ,002
5
47
0.995
47
0,986
5
5
47
0.997
No.
of
Stages
3.11
3.50
4.26
4.15
4.00
2.68
3.28
3.84
3.67
3.68
3.71
4.00
H.E.T.S. Solvent
in
Inches
8.73
7.75
6.37
6.55
6.81
10.10
8.30
7.08
7.40
7.40
7.35
6.80
Rate
Faotorc
0.762
0.865
1.097
1.029
1,108
0.751
0.881
1.040
0.998
0.984
0.962
1.022
Ad-
I%?.%
Continuous phase.
of column.
Solvent rate factor is equal to (actual solvent rate/standard solvent rate)o.*'.
Table II.
Run
NO.
2b
35
37
4b
10
15
32
39
65
66
67
68
3 b
8
16
25
31
34
40
58
59
60
5b
11
12
33
56
57
13
17
24
28
41
18
19
21
29
27
a
b
Feed Flow
Acid Concentrations, Wt. yo Acetic
Ketone
Acid
Ex~ ~ f f i CU.
Ft./Hr.
Ketone
tract
nate
feed
feed
9.40
12.4
6.4
0
17.8
6.84
12.5
10.0
19.6
0.1
7.62
17.6
13.0
7.6
0.2
10.15
12.3
5.0
18.2
0.4
9.31
14 .%
6.0
20.4
0.2
8.26
13.8
7.2
19.0
0.4
8.45
20.1
13.3
5.5
0.2
10.01
12.4
4.3
19.1
0.4
9.14
13.4
6.0
20.6
0.3
8.93
13.9
6.1
20.5
0.3
9.42
13.4
5.5
20.5
0.3
8.72
18.9
1
2
.
0
7
.
2
0.3
8.97
15.3
7.8
19.0
2.2
7.70
1
5
.
0
6
.
0
19.2
0.5
8.10
13.3
7.0
18.0
0.9
9.84
1
1
.
9
6
.
8
18.2
0.4
8.37
13.8
6.0
19.9
0.2
6.84
14.4
4.6
19.7
0.1
10.48
12.0
5.2
20.4
0.2
9.19
12.6
5.7
18.5
0.1
9.55
12.4
5.8
18.5
0.1
9.39
12.7
5.5
18.6
0.1
8.54
13.6
5.5
18.7
0.3
9.18
14.2
6.0
19.4
0.2
9.42
14.4
5.4
20.3
0.2
7.66
13.6
7.7
20.1
0.2
8.30
15.6
6.0
22.2
0.1
8.11
15.5
6.1
22.2
0.1
9.42
13.9
5.3
20.3
0.2
8.56
13.6
5.0
19.0
0.6
8.76
14.6
5.0
20.4
0.5
8.29
14.1
5.6
19.2
0.3
9.73
11.7
5.8
20.3
0.2
8.34
14.4
6.8
19.2
0.4
8.34
13.8
4.4
19.2
0.4
7.90
13.4
5,3
18.5
0.3
8.53
13.2
5.2
18.4
0.3
8.29
15.0
4.4
20.8
0.2
Rates,
8s. Ft. Cycles/
Acid'"
minute
9.16
17
7.54
17
17
7.30
29
7.85
7.94
29
8.65
29
8.15
29
29
7.85
29
7.95
29
8.45
29
8.10
8.52
29
9.00
47
47
8.05
47
8.10
8.00
47
8.20
47
47
7.57
47
9.30
8.23
47
8.69
47
47
8.60
8.69
78
8.23
78
78
7.85
78
8.60
78
8.35
78
8.16
7.93
88
7.63
88
7.69
88
7.76
88
88
8.49
147
8.27
8.27
147
7.55
147
147
8.89
252
7.37
Displacement,
mm.
4.5
7.0
8.0
5.5
5
3.0
9.5
9.0
5.0
10.0
7.5
2.5
5.5
6.0
3.0
1.5
10.0
9.0
6.0
8.5
5.0
7.0
6.0
5.0
5.0
8.5
3.0
7.0
5.5
2.5
2.5
1.5
6.0
3.0
1.5
1.5
2.5
1.0
Material
Balance
Accuracy
Measured
Wt. Out/
Calod. Wt. I n
No.
of
Stages
3.23
3.03
4.70
4.66
4.61
4.18
4.14
4.39
3.75
4.10
4.04
2.90
8.40
6.22
4.88
3.22
3.30
4.15
5.31
4.33
4.00
4.42
5.78
5.90
5.24
3.27
4.52
4.40
4.68
6.23
6.05
6.12
4.10
6.00
6.65
5.92
5.97
8.25
H.E.T.S.
in
Inches
10.0
9.00
5.78
6.76
5.97
6.54
6.50
6.20
7.25
6.63
6.74
9.40
3.84
5.04
5.61
8.43
8.20
6.55
5.10
6.42
6.80
6.15
5.44
4.67
5.25
8.30
6.00
6.20
5.90
4.40
4.48
4.43
6.60
4.54
4.12
4.60
4.56
3.30
Solvent
Rate
Factor
Adjusted
H.E.T.B.
10.15
8.85
5.43
7.08
6.74
6.33
6.34
6.45
7.29
6.62
6.85
9.26
3.83
4.76
5.40
8.81
8.10
6.45
5.28
6.47
6.96
6.25
5.35
4.71
5.54
7.81
5.82
5.99
6.00
4.33
4.44
4.28
6.77
4.42
4.02
4.38
4.48
3.20
Continuous phase.
Runs 1 through 6 were made with packed height of 31.5 inches; packed height in all other runs was 27.2 inches.
1154
+m u
c%
SAMPLE
S4M
Hi
PACKED
COLUMN
W
Figure
1.
MERCURY T R A P
Layout
of countercurrent
apparatus
extraction
Figure 2.
Packed Column
About 100 experimental runs were made with the packed
column, mostly with the system methyl isobutyl ketone-acetic
acid-water. The main portion of the study was made with feed
June 1955
Yu
G 7
vi
2 6
H.E.T.S. calculated for runs 59, 81, 82, and 83 corrected for
the effect of varying solvent rate as already established, are
plotted in Figure 3. The efficiency of the column is shown to be
almost independent of the continuous-phase rate when the column
is pulsed. The influence of the continuous-phase rate on the holdup in the column as well as the turbulence is reduced to almost nothing with pulsation. The holdup becomes more a function of the up-and-down motion than the flow rates. All the
results for the packed column, except those concerned with
flooding, have been adjusted t o a constant solvent feed rate of 9
cubic feet per hour per square foot.
I n order t o establish how much the efficiency can be improved
and how the pulse can best be applied, 38 runs were made at 7
frequencies using a range of amplitudes from 1 to 10 milimeters.
One pulsator afid approximately constant feed concentrations
and rates were used for all of these runs. The results are shown
in Table I1 and Figure 4. As the amplitude is increased a t any
one frequency the H.E.T.S. a t first decreases, reaches a minimum,
and then increases as the flooding characteristics are approached.
When the flooding point has been reached, the column becomes
inoperative, and the condition represents a degree of agitation
which gives drop sizes too small to coalesce readily. The flooding point under pulse conditions probably varies greatly with the
interfacial tension. Different systems and the presence of
surface active impurities should be studied in future investigations. The curved lines in Figure 4 are cross-plotted in Figure
5 to show the effect of frequency.
I N D U S T R I A L A N D E N G I N E E R I N G CHEMISTRY
1155
Figure 4.
Table Ill.
FREQUENCY
CYCLES PER MINUTE
Figure 5.
Performance of Pulsed Packed Column with Constant Feed Rates Using Proportioning Pump
Pulse
Run
No.
42
43
44
45
46
47
48
49
50
51
52
53
54
55
a
feed
0.2
0.2
0.1
0.1
0.1
0.2
0.2
0.1
0.1
0.1
0.3
0.2
0.2
0.1
19.6
19.6
19.8
19.2
19.3
19.5
19.4
18.2
18.2
18.1
18.9
20.0
20.0
20.3
14.0
13.9
13.4
13.0
13.2
13.6
13.8
11.4
12.0
12.4
13.2
13.8
14.0
15.2
5.2
5.0
5.7
5.4
4.6
5.2
5.0
6.5
5.1
5.5
4.9
4.2
4.2
3.8
8.71
8.76
8.64
8.46
8.47
8.76
8.83
7.85
7.91
8.77
8.29
8.71
7.69
7.90
Cycles/
minute
55
56
55
80
80
80
80
80
80
135
135
135
135
135
Displacement,
mm.
4.0
3.0
2.0
4.0
3.0
2.5
1.5
0.3
0.8
0.8
1.0
1.5
2.0
2.5
Material
Balance
Accuracy
Measured
Wt. Out/
Calcd. Wt. In
No.
of
Stages
H.E.T.S.
In
Inches
Solvent
Rate
Factor
Adjusted
H.E.T.S.
0.996
0,994
0.996
0.998
0.998
0.997
0.997
1,000
1.000
0.995
0.998
0.998
1,000
0.998
5.61
5.51
4.14
4.32
5.14
5.07
5.62
3.24
4.29
4.45
5.68
5.90
6.20
5.80
4.84
4.92
6.56
6.29
5.28
5.35
4.83
8.39
6.35
6.10
4.78
4.61
4.38
4.70
1.006
1.006
1.007
1.022
1.029
1.014
1.018
1.011
1.012
1.002
1.006
1.047
0.994
0,992
4.87
4.95
6.60
6.43
5.43
5.43
4.91
8.48
6.43
6.11
4.81
4.82
4.35
4.66
Continuous phase.
1156
Table IV.
it. Out/
No.
of
Stages
H.E.T.S.
In
Inches
Solvent is 10% methylene dichloride in ethyl acetate: acid feed is acetic acid in water.
b Continuous phase.
Run flooded-results
estimated.
.
Table V.
Ketone
8.96
13.92
14.17
14.17
12.60
8.30
12.30
Acida
8.14
12.80
14.40
13.90
14.16
8.35
13.72
Pulse
Material Balance
DisplaceAccuracy
ment, Measured Wt. Out/
mm.
Calcd. Wt. I n
0
0.997
0
0
0.999
0
0
0.998
47
6
47
6
0 : 990
78
3
0.991
78
3
...
Cycles/
minute
0
NO.
of
Stages
2.73
3.53
3.69
6.41
4.79
4.52
5.68
H.E,T.S.
in
Inches
10.00
7.70
7.390
4.25C
5.69b
6.00
4.79d
FREQUENCY
CYCLES PER MINUTE
1157
Run
.
I
2
3
AMPLITUDE, MILLIMETERS
Material Balance
Accuracy
Measured Wt. Out/
Calcd. Wt. In
No.
Av. Plate
Efficiency,
of
Stages
4.95
6.25
3.33
6.20
5.31
7.63
2.41
2.49
2.60
2.70
2.81
2.10
2.24
3.02
2.58
2.65
2.71
2.38
3.04
3.27
3.26
3.00
2.35
1.75
2.08
3.10
45.01
56.8b
30.01
56.4b
48.3b
70.0b
21.9
22.6
23.7
24.6
25.5
19.0c
20.3
27.6
23.5
24.1
24.5
21.6
27.6
29.7
29.6
28.2
21.4
15.9
18.9
28.2
1158
36
Figure
I
2
4
6
e
AMPLITUDE, MILLIMETERS
IO
Conclusions
Packed Column
1. The application of pulsation to a packed column is a practical method for efficiency improvement. The height of packed
Literature Cited
Benedict, iM.,
IND.
ENQ.CEIEM.,45, 2372 (1953).
Callahan, E. W., and Geyh, C. A., Effect of Pulsation on 8
Sieve-Plate Extraction Column, Senior Project Report.
Cornell University, June 1953.
Chantry, W. A., Application of Pulsation to Liquid-Liquid
Extraction, Ph.D. Thesis, Cornell University, June 1953.
Chem. Eng.,61, No. 6, 282 (1954).
Chem. Eng. News, 32, 350 (1954).
Chemical Week, 69, No. 24, 32 (Dec. 15, 1951).
Cohen, R. M., and Beyer, G. H., Chem. Eng. Progr., 49, 279
(1953).
Rich, W., Ross, K., and Mehler, G., Agitation in a LiquidLiquid Extraction Column, Senior Project Report, Cornell
University, June 1952.
Robinson, J., U. S. Patent 2,072,382 (March 2, 1937).
Scheibel, E. G., Chem. Eng. Progr., 44, 681, 771 (1948).
Scheibel, E. G., IND.
ENG.CHEM.,42, 1497 (1950).
Scheibel, E. G., and Karr, A. E., Ibid., 42, 1043 (1950).
Sege, G., and Woodfield, F. M., Chem. Eng. Progr., 50, 396
(1954).
ACCEPTED
March 28, 1956.
HOMER
F. JOHNSON
The power required to pulse a liquid-liquid extraction column is determined by the static head
of the liquid system, the acceleration and deceleration forces on the liquid system, and the friction losses. The theoretical total power that must be applied to the liquid-liquid system b y
the pulser i s given by the equation
where the equation for y defines the cyclic motion imparted to the liquid system by the pulse
generator. Power input data obtained on a 50-foot pulse column 24 inches in diameter are
presented, as well as information on development of the power formula and the means of
experimentally evaluating the formula.
HE use of pulsed towers in continuous, countercurrent liquidliquid extraction frequently leads to improved performance
over conventional types of towers such as the packed tower.
The pulse action is provided by aome sort of mechanical pulse
generator, usually a reciprocating piston-type unit. Pulsing
June 1955
the fluid in the tower has the effect of putting energy into the
liquid-liquid system beyond that which is due solely to the action
of gravity on the dispersed phase particles. This additional
energy probably benefits performance by increasing effective interfacial area as well as increasing turbulence in the system.
1159