You are on page 1of 7

Application of Pulsation to

Liquid-Liquid Extraction
W. A. CHANTRY', R. L. VON BERG,

AND

H. F. WIEGANDT

Cornell Universify, fthoco, N. Y.

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

N E of the requirements for effective liquid-liquid extraction is


thorough mixing of the two phases. I n a batch extraction

this is easily achieved by agitating the two liquids and then


allowing them to settle and separate. By suitable arrangement
of mixing vessels and settling tanks it becomes possible to operate
stagewise and countercurrently. However, if many repeated
extractions are necessary this method is likely t o be cumbersome
and expensive.
In order to reduce the number of pieces of equipment needed
for countercurrent extraction it has become common to use a
column, usually a packed column, with counterflow of two liquid
streams through it. A large number of variations in the design
of countercurrent extraction columns have been summarized in
the literature (18, 19). With but few exceptions the energy for
mixing the liquids in these columns has been obtained solely from
the gravity force resulting from the difference in density between
the two phases. The exceptions, all reported within the last few
years, have used several different methods for supplying additional energy for added internal agitation.
A column with a series of mixers and settling areas was reported
by Cornish, Archibald, Murphy, and Evans (8) as early as 1934.
The following year, Van Dijck (SO) patented a column in which a
set of perforated plates was moved up and down with respect
to t,he column to provide agitation. Another apparatus patented
(16)was designed to oscillate the entire column. Ney and Lochte
( 1 9 ) and Maycock ( 1 7 ) tried spinner columns consisting of a
smooth revolving cylinder in a slender column.
There have been several reports (23-95) on the Schiebel-type
columns. These columns consist of alternate packed and mixing
sections. Each mixing section includes a paddle driven a t high
speed from a central shaft. I n some instances the performance
of a combined mixing section and a packed section exceeded one
theoretical stage.
Robinson (2%)patented a similar unit using distribution plates
between packed sections. Oldshue and Rushton (10)reported
the results of their investigation of a column constructed with
mixing sections made from an impellor and vertical baffles
separated by perforated compartmenting plates. Gallo and
Hartvigsen (11) patented a mixer-settler continuous countercurrent extractor which used sections in which the liquids were
mixed with propellers separated by horizontal-tube settling areas.
Davis and Hicks ( 9 ) review a number of mixer-settler devices.
Present address, Shell Chemical Corp., Martinez, Calif.

June 1955

Recent news items (4,5) inchate continued interest in the


development of other mechanical arrangements.
The study of the effect of pulsation on liquid-liquid extraction
in packed and sieve-plate columns was initiated a t Cornell University in February 1949. Two brief descriptions of this work have
appeared in the literature ( 6 , S I ) . Both liquid phases were
moved up and down together within the column by connecting a
device similar to a reciprocating piston to the bottom of the
column. Studies have been made by Goundry and Romero ( I S ) ,
Marsland and Buckner ( 1 6 ) , Smith and Caplan (28), Rich,
Mehler, and Ross (11), Gilbert and Huntress ( 1 2 ) ,and Callahan
and Geyh ( 2 ) . The present study (5)was completed in June 1953.
I n 1952 an investigation of the effect of pulsation on the
operation of a packed extraction column was reported by Feick
and Anderson (10). They reported considerable improvement
in extraction efficiency with pulsation when extracting benzoic
acid or acetic acid from toluene with water. Cohen and Beyer
( 7 ) reported on the effect of pulsation on sieve-plate columns.
Extraction devices considered by the Atomic Energy Commission are mentioned by Benedict ( I ) and by Sege and Woodfield (16).
The earlier studies at Cornell University had indicated that
extraction efficiency could be greatly increased by pulsation.
First determined in this study using a packed laboratory column
were the best operating conditions of pulse frequency and amplitude for one 3-component system a t a constant feed rate. Then
the effect of varied feed rates and effect of pulsation on flooding
capacity were established. Preliminary considerations were
also given t o variations in the pattern of the pulse stroke. A
series of runs was initiated to determine the best operating conditions and attainable efficiencies for a pulsed sieve-plate column.

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

INDUSTRIAL AND ENGINEERING CHEMISTRY

1153

ENGINEERING, DESIGN, AND PROCESS DEVELOPMENT


Table 1.

Run

No.

Acid Concentrations, Wt. % Acetic

Feed Flow Rates,

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

Performance of Pulsed Packed Column with Varied Feed Rates

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.*'.

b Measured in unpacked section


c

Table II.

Performance of Pulsed Packed Column with Constant Feed Rates


Pulse

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.

of sieve plates were used; one with twenty-four 3/Ba-inchholes and


the other with twenty-four j/04-inch holes. Two types of
pulsators were used to supply the added agitation. The unit
especially designed and used for this project was fundamentally
a pair of copper bellows driven by an electric motor through two
sets of speed change pulleys and an adjustable cam. Frequencies
from 0 to 300 cycles per minute were available a t amplitudes,
measured in the unpacked section, ranging from 0 to 10 millimeters. The other pulsator, used to check the results was a
proportioning pump with its valves removed and inlet line sealed.
The feed tanks were two &gallon carboys. Each feed line included a rotameter and a surge tank which eliminated the effect
of the pulse on the feed control. The raffinate was removed
through the vented interface-control leg. The solvent feed
entered about 1 inch below the packing support or the bottom
sieve plate; the pulse line entered 4 inches below this plate.
The pulse was transmitted through a mercury-filled U-tube
which sealed the column liquids from the pulsator. All of

1154

the lines were of borosilicate glass joined with neoprene tubing


on the acid side and polyvinyl alcohol tubing on the solvent side.
Two 3-component liquid systems were used in the tests:
methyl isobutyl ketone-acetic acid-water and ethyl acetate
solvent-acetic acid-water.
I n nearly all the runs a 2001, by weight acetic acid solution fn
water was extracted by neutral solvent with the water phase
continuous and the interface held a t the top of the column.
The feed solutions were mutually saturated with respect to water
and solvent. The column was allowed to run until the composition of the product streams, as checked periodically by titration
with 0.1N sodium hydroxide, remained constant for at least
30 minutes. Then the exit streams were collected for timed
intervals and the accumulated volume analyzed. With these
data the material balance could be checked for each run.
The results were used to calculate the height equivalent to a
theoretical stage (H.E.T.S.) for the packed column and the
average plate efficiency in the sieve-plate column. The theoreti-

INDUSTRIAL AND ENGINEERING CHEMISTRY

Vol. 47, No. 6

PULSATION AND VIBRATION

+m u

c%

SAMPLE

S4M

Hi

PACKED
COLUMN

W
Figure

1.

MERCURY T R A P

Layout

of countercurrent
apparatus

extraction

cal stages were estimated analytically using the method of Hunter


and Nash (14). The equilibrium data for the system methyl
isobutyl ketone-acetic acid-water were those reported by Sherwood, Evans, and Longcor ( 8 7 ) . The ethyl acetate solvent was
a special solution furnished by the Hercules Powder Co.; and,
since no equilibrium data were available, these were determined
experimentally and correlated for use in the calculation of
theoretical stages.

SOLVENT FEED RATE


CUBIC FEET PER K)UR PER SQUARE FOOT

Figure 2.

Effect of solvent rate on stage


height

The method of stage calculetion was accurate to the nearest


0.25 stage, and the material balances were all checked to within
5 % of closing.

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

rates constant at approximately 60% of the calculated flooding


capacity. Several runs were made with these feed rates and no
pulsation to determine the H.E.T.S. under conventional conditions. With feed rates of 8 cubic feet per hour per square foot
of unpacked area for 20% acetic acid and 9 for methyl isobutyl
ketone the H.E.T.S. was 10 inches.
I n three series of runs the feed rates were varied t o determine
the effect of this variable with pulsation. The data and calculated results of these runs are shown in Table I. The H.E.T.S.
calculated for runs 72 through 75 made at a pulse rate of 54 cycles
per minute and a 6-mm. displacement and runs 76 through 80
made a t a pulse frequency of 29 cycles per minute and 6-mm.
displacement are plotted in Figure 2 as a function of the dispersed-phase flow rate. The results based on runs in which only
the solvent feed varied indicate that the H.E.T.S. varies inversely
with the volumetric solvent rate raised to the 0.37 power. Using
a solvent feed rate of 9 cubic feet per hour for each square foot of
cross-sectional area as a standard, the results are also expressed
in Table I for the calculated H.E.T.S. values a t this flow rate.
This effect of changing the dispersed phase rate is less with pulsation than generally reported for conventional packed columns.
Lower stage heights are expected with increased rates as the
result of greater turbulence in both phases. With pulsation, the
turbulence comes more from external agitation than from the flow
of liquids; thus, the effect of the rate change is less.

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

ENGINEERING, DESIGN, AND PROCESS DEVELOPMENT

Figure 4.

Effect of pulse amplitude on stage

There are two effects of the increase in amplitude or frequency


which cause an increase in efficiency. The drop size is reduced,
slowing their rate of rise and increasing the holdup of the dispersed
phase. Therefore, greater interfacial area is available for mass
transfer. At the same time, because of the greater turbulence in
both phases, the rate of mass transfer to and from the interface
increases. Several authors ( 2 7 ) have determined from studies of
extraction by single drops that 25 to 60% of the extraction in a
spray column takes place during drop formation and coalescence.
Observations of the pulsed column in operation indicate there
is a large amount of this action, especially when the holdup of the
dispersed phase is high. Thus, the increased holdup and turbulence both contribute to the constant formation of fresh interfaces.
From Figure 4,the values of the frequency and amplitude necessary to obtain an H.E.T.S. of 7 inches were obtained and
plotted in Figure 6. The equation of the line drawn to represent
the points is
Amplitude = 10000 (Frequency)-*

time. At 252 cycles per minute this


product is 17.6 millimeters per minute
and a t 47 cycles per minute it is 164.5
millimeters per minute. This indicates
that the power required is much larger
a t the lower frequency. The average
velocity in the column is directly proportional to the product of the amplitude,
and frequency and friction losses are
greater a t higher velocities. The conclusion drawn is that less power will be required if the combination of the highest
frequency and the lowest amplitude that
will give the desired results is used. This
assumes that there is no regain of energy
from a balancing hydraulic leg or similar
device. Actually the power requirements, even for a column several feet in
diameter, are quite small and more important engineering considerations are
those of pump size and the vibrational
stresses a t higher frequencies. This may
very likely lead to a compromise for
the increase in efficiency attained, power
height
consumed, and the stresses placed on
the equipment.
The dashed line in Figure 4 describes the limits of operability
for the system studied. A similar line through the minima of the
curves would represent conditions for maximum efficiency. The
facts that have been established are
1. Pulsation does improve the efficiency by as much as 300%.
2. There is an optimum amplitude that may be used with
each pulse frequency to obtain the best efficiency improvement.

where the amplitude is in millimeters and the frequency in cycles


per minute. The amplitude is approximately proportional to the
reciprocal of the frequency squared. The product of the frequency and amplitude a t any of the conditions on the line is a
measure of the energy needed to raise the column of liquid per unit

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

Acid Concentrations, Wt. % Acetic


ExRaffifeed
tract
nate

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

Effect of pulse frequency on stage height

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

Feed Flow Rates,


CU. Ft./Hr. 8s. Ft.
Ketone
Acida
9.15
9.16
9.19
9.55
9.72
9.35
9.45
9.27
9.29
9.04
9.14
10.20
8.87
8.80

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

INDUSTRIAL AND ENGINEERING CHEMISTRY

Vol. 41, No. 6

PULSATION AND VIBRATION

Table IV.

Performance of Pulsed Packed Column with Another System


malance
ICY

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.

Performance of Packed Column Near Flooding Point

Acid Concentrations, Wt. %


Acetic
Ketone
Acid
RaffiNO.
feed
feed
Extract
nate
7.2
19.4
12.0
105
0.2
11.9
6.2
114
0.2
18.1
6.8
12.3
115
0.2
18.1
4.5
19.2
13.6
116
0.4
13.0
4.8
117
0.4
19.4
56
0.1
22.2
15.6
6.0
118
0.4
19.4
13.4
4.6
a Continuous phase.
b This run a t highest rate possible without flooding.
This run flooded and results are estimated.
d This run incomplete-apparent
equilibrium is reported.
Run

Feed Flow Rates,

cu. Ft./Hr. sq. Ft.

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

3. Increasing either frequency or amplitude first improves t,he


extraction efficiency until an optimum is reached, then the
efficiency is reduced until the column floods.
4. High frequencies and short amplitudes give the largest
improvement in efficiency.
5 . Conditions of high frequency and short amplitude consume
less power input for the same efficiency improvement than low
frequency and greater displacement.
Two series of runs were made independently to check these
facts. First, the pulsator was replaced with a proportioning
pump which gave a sharp up-pulse as compared to the sine wave
transmitted from the pulsator. Runs were made at three frequencies-55, 80, and 135 cycles per minute-and displacements
from zero to 4 millimeters. Table I11 and Figure 7 show the
results. The results agree well with the previous results. The
sharper pulse gives no noticeable improvement in efficiency.
What the effect of changing the pulse pattern would be in other
systems, particularly if there exists a large dirference in viscosity
between the two phases, remains to be established.
Next, a series of 17 runs was made using another 3-component
system, ethyl acetate solvent-acetic acid-water. The density
difference between the phases was much lower in these runs so the
throughput was reduced. Table IV and Figure 8 show the results.
I n all these runs the holdup of the dispersed phase, again the
solvent, was quite large, and operation was near the flooding
point. I n runs 98 and 99 some of the solvent phase was being
carried out with the raffinate and steady-state conditions were
not attained. I n general, the shape of the curves in Figure 8
and the magnitude of efficiency improvement agrees quite well
wit,h previous results.
To conclude the packed column study, several runs were made
to determine the effect of pulsation on maximum throughput.
The results of these runs are listed in Table V. Run 115 was
made at the highest rates possible without flooding the column
June 1955

FREQUENCY
CYCLES PER MINUTE

Figure 6 . Relation of puke amplitude and


frequency for an H.E.T.S. of 7 inches

with no pulsation. The H.E.T.S. for this run was calculated to


be 7.39 inches.
Run 117 was made a t the highest possible rates without flooding a t a frequency of 47 cycles per minute and an amplitude of
6 millimeters. A total hourly rate per square foot of column
cross section of 26.57 cubic feet of liquids were accommodated during this run as compared to 28.57 during run 115. This represents a 6% reduc$ion in maximum throughput when the column
is pulsed. For run 118 a t 7 8 cycles per minute the total hourly
throughput was 26.02 cubic feet per square foot or equivalent
to 8.9% less than the capacity without pulsation. *
The reduction in capacity with increased agitation is surprisingly little even though smaller drops are produced in the packing
and the holdup increases. The flooding point is defined as the
condition a t which the holdup is too large to accommodate increases in either phase rate. Any increase will cause the dis-

INDUSTRIAL AND ENGINEERING CHEMISTRY

1157

ENGINEERING, DESIGN, AND PROCESS DEVELOPMENT


Table VI.

Performance of a Pulsed Sieve-Plate Column

Acid Concentrations, Wt. % Acetic


Feed Flow Rates,
Pulse
cu.Ft*/Hr*sq* Ft- Cycles/
Amp.,
Ketone
Acid
RaffiNo.
feed
feed
Extract
nate
Ketone
Acid5
minute
mm.
0.6
9
18.4
13.1
6.2
8.67
8.35
47
2.0
14
20.8
0.1
13.30
47
2.5
6.5
15.8
12.70
22
0.3
19.8
7.6
7.87
13.4
8.25
80
1.5
47
20.1
23
2.1
0.3
7.84
12.2
10.37
1.6
26
0.3
20.2
1.8
8.21
2.0
10.8
14.73
30
0.3
20.3
14.0
2.7
7.55
2.0
11.68
20.6
61
0.2
6.94
11.4
6.9
9.24
5.5
62
0.2
20.7
12.0
7.2
6.0
8.55
8.88
0.2
20.5
63
12.4
8.63
7.5
8.99
3.5
0.2
20.5
64
12.6
7.4
9.06
8.15
2.0
70
0.4
20.4
13.1
2.0
8.0
8.65
8.52
20.5
71
0.3
11.9
9.1
8.25
8.50
3.0
19.0
78
0.1
12.0
7.30
8.33
3.0
9.0
0.4
19.1
84
10.2
7.80
5.0
11.08
3.0
19.1
9.4
4.7
3.0
0.4
7.73
12.82
85
0.3
19.5
9.0
8.30
3.7
13.90
3.0
86
0.3
19.5
13.2
87
12.9
3.0
7.27
15.99
0.2
18.9
7.6
4.0
17.60
4.6
106
8.05
0.4
18.9
8.5
4.0
3.1
107
16.82
8.38
1
9
.
6
4.0
0
.
2
5
.
4
11.9
17.15
108
13.18
19.6
13.6
4.0
0.2
8.6
109
16.67
18.92
1
9
.
1
0
.
4
12.3
4.0
7.3
8.24
110
8.50
19.1
0.4
11.6
6.0
8.6
8.05
8.90
112
18.3
10.4
0.2
9.1
113
6.0
8.27
9.25
19.4
12.4
0.4
6.0
119
10.2
8.74
7.20
19.4
0.4
4.0
6.70
120
2.7
8.1
15.37
Continuous phase.
b These runs were made using plates with a/sa-inch holes; remainder used plates with s/winch holes.
c Ketone phase was continuous in this run with interface below bottom plate.

Run

.
I

2
3
AMPLITUDE, MILLIMETERS

Figure 7. Effect of pulse amplitude using a


proportioning pump

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

poorer plate efficiencies. The highest attainable average plate


efficiency was about 30y0. Several series of runs were made to
determine the best operating procedure. However, complete
coalescence of the dispersed solvent phase below the plates was
not attained, and the column never performed effectively with the
larger hole size.
These results lead to the conclusion that the best operation of
a pulsed sieve-plate column is obtained with a combination of
high holdup and sufficient turbulence. Plates with smaller holes
appear best for both effects. Sufficient frequency and amplitude
must be supplied for turbulence and feed rates must be maintained a t a high enough level for sufficient holdup. The column
must be operated near the flooding point t o have a coalesced
dispersed phase layer a t each plate. Any change in operating
characteristic8 will cause the column either to flood or to lose
one of the liquid layers.

persed phase to become continuous a t some point in the column.


Usually a layer of solvent first appeared below the packing and
gradually filled the free area a t the bottom of the column.
Sieve-Plate Column

Exploratory runs were made with a pulsed sieve-plate column.


The results of these runs appear in Table VI. For these runs, the
average plate efficiency obtained by dividing the number of
theoretical stages by the number of plates is reported instead of
the H.E.T.S.
Runs 9, 15, 22, 23, 26, and 30 were made using the sieve plates
with twenty-four a/,,inch
perforations. These results were
unsatisfactory and inconsistent; however, efficiencies as high as
70% were obtained. Corrosion and clogging of the small holes
made use of these plates impractical for the solutions used. Two
or three plates appeared to flood while others were operating
satisfactorily. The pressure drop through the plates was quite
high. Considering that numerous additional holes could have
been drilled it is obvious from comparative thrpughputs that the
allowable capacity for sieve-plate construction is inherently
greater than fqr packing.
When proper operation was obtained, a layer of solvent phase
was held under each plate and only rose in the column on the
up-pulse. On the down-pulse a jet of acid phase entered the
solvent phase. Effectively, two mixing and settling operations
are obtained a t each plate. The balance of the runs made with
plates with holes enlarged to a diameter of /e4 inch showed

1158

36

Figure

I
2

4
6
e
AMPLITUDE, MILLIMETERS

IO

8. Effect of pulse amplitude with a


different system

No investigation was made of the sieve-piate column under


conditions allowing no coalescence of the dispersed phase under
the plates. However, many of the runs using the 6/6&-inchholes
approached this condition. When the column is operated in
this manner the sieve plates serve the same function as packing.

Conclusions
Packed Column
1. The application of pulsation to a packed column is a practical method for efficiency improvement. The height of packed

INDUSTRIAL AND ENGINEERING CHEMISTRY

Vol. 47, No. 6

PULSATION AND VIBRATION


section required is reduced as much as three times when the
column liquids are pulsed.
2. Optimum operating conditions can be obtained by varying
both frequency and amplitude of pulse.
3. Greater efficiency can be obtained with the proper low
amplitude a t high frequencies than is possible a t low frequencies.
4. The maximum throughput is reduced slightly ( 5 t o 1 O o J ~ )
when the column is pulsed.
5 . Changes in feed rates have less effect on the efficiency when
pulsation is used than with the usual packed column operation.
Sieve-Plate Column
1. Average plate efficiencies as high as 70% can be obtained
in pulsed sieve-plate columns.
2. High throughput rates compared t o packed column capacity may be used with high efficiency.
3. Smaller perforations are more efficient but more a p t to
corrode and clog, and have reduced capacity.

Gallo, S. G., and Hartvigsen, B. (to Standard Oil Development


Co.), U. S. Patent 2,562,783 (July 31, 1951).
Gilbert, T. E., and Huntress, A. R., Pulsation in a Packed
Liquid-Liquid Extraction Column, Senior Project Report,
Cornell University, June 1953.
Goundry, P. C., and Romero, V. M., Effect of Agitation on
Liquid-Liquid Extraction in a Packed Column, Senior
Project Report, Cornell University, Feb. 1950.
Hunter, T. G., and Nash, A. W., J . SOC.Chem. Ind., 53, 95T
(1934).

I. G. Farben, British Patent 457,552 (Nov. 25, 1936).


Marsland, D. B., and Buckner, L. R., Jr., Effect of Agitation
on Liquid-Liquid Extraction in a Packed Column, Senior
Project Report, Cornell University, June 1951.
Maycock, R. L. (to Shell Development Co.), U. S. Patent
2,474,007 (June 21, 1949).
Morello, V. S., and Poffenberger, N., IND.
ENG.CREM.,42, 1021
(1 950).

Ney, W. O., and Lochte, H. L., Ibid., 33, 825 (1941).


Oldshue, J. Y . ,and Rushton, J. H., Chem. Eng.Progr., 48, No. 0,
297 (1952).

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).

Coinish: R. E., Archibald, R. C., Murphy, E. A., and Evans,


H. M., IND.
ENG.CHEM.,26, 397 (1934).
Davis, M. W., Jr., Hicks, T. E., and Vermeulen, T., Chem. Eng.
Progr., 50, 188 (1954).
Feick, G., and Anderson, H. M., IND.ENG. CHEM.,44, 404
(1952).

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).

Sherwood, T. K., Evans, J. E., and Longcor, J. V., IND.ENQ.


CHEM.,31, 1144 (1939).
Smith, H. M., and Caplan, R. H., Effect of Agitation on LiquidLiquid Extraction in a Sieve-Plate Column, Senior Project
Report, Cornell University, June 1951.
Treybal, R. E., IND.ENG.CHEM.,45, 50 (1953).
Van Dijck, W. J. D., U. 9. Patent 2,011,186 (August 13, 1935).
Von Berg, R. L., and Wiegandt, H. F., Chem. Eng., 59, No. 6,
189 (1952).
RBCEIVED
for review December 20, 1954.

ACCEPTED
March 28, 1956.

Power Requirements for Pulse


Generation in Pulse Columns
A. CARLETON JEALOUS
O a k Ridge Nafional laborafory, O a k Ridge, Tenn.

HOMER

F. JOHNSON

Deparfmenf o f Chemical Engineering, Universify o f Tennessee,


Knoxville, Tenn.

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.

INDUSTRIAL AND ENGINEERING CHEMISTRY

1159