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Edited from DBM original by HJT 1 Fall 2011

ChE 4162 Liquid-Liquid Extraction Operating Manual


Introduction
Liquid-liquid extraction is a relatively new unit operation in industry, though it has been used for
centuries in laboratories. It is used to separate materials that cannot easily be separated by other
methods. The driving force for mass transfer is the difference in solubility of one material (the
solute) in two other immiscible or partially miscible streams (the feed and the solvent). The feed
and solvent streams are mixed and then separated, allowing the solute to transfer from the feed to
the solvent. Normally, this process is repeated in successive stages using counter-current flow.
The solute-rich solvent is called the extract as it leaves, and the solute-depleted feed is called the
raffinate. When there is a reasonable density difference between the feed and solvent streams,
this can be accomplished easily using a vertical column.
Apparatus
The York-Scheibel liquid
extraction column shown in Figure
1 can be used to perform a variety
of liquid extraction operations.
Feed can be introduced at the
bottom of the column (11 stages)
or at the middle of the column (6
stages). In this experiment, you
will extract isopropanol (8-to-10
wt %) from Isopar-E (a mixture of
C8-to-C10 hydrocarbons with
physical and chemical properties
almost identical to n-nonane) using
pure water as the solvent.
The laboratory extraction unit
consists of a 2" I.D. Pyrex column,
with 11 extraction stages, each
consisting of a one-inch mixing
section and a four-inch wire mesh
packing (coalescing) section. The
column is mechanically agitated by
horizontal thrust agitators mounted
on a 3/16" diameter shaft. A
variable speed motor, with a
control knob and digital readout on
the control panel, controls the
speed of the agitator. Rotameters
on the feed and solvent inlets are
used to measure those flow rates.
Flow rates of the extract and
raffinate can be measured with a
graduated cylinder and stopwatch.
Edited from DBM original by HJT 2 Fall 2011
Rotameter Equations
1

The following equations relate rotameter readings to volumetric flowrates:
2
2.04 0.00170
f f f
F R R = (1)
2
1.62 0.00143
s s s
F R R = (2)
Where F
f
is the feed flow rate (~10 wt% IPA) in ml/min,
R
f
is the feed rotameter reading,
F
s
is the solvent flow rate in ml/min, and
R
s
is the solvent rotameter reading.

These calibrations are useful for planning and trial run purposes. Inasmuch as the feed is variable
in composition, the feed rotameter calibration is subject to an additional disclaimer.
Equilibrium Data for Water/Isopropanol/n-Nonane
In this experiment, we assume the properties of n-Nonane are a good approximation of Isopar-E
for equilibrium data purposes. The ternary Water/Isopropanol/n-Nonane exhibits Type I
equilibrium behavior at room temperature. The equilibrium data are in your groups directory of
the ChE apps drive.
Operating Procedure
1. Bleed a small volume from the raffinate tank and check for water. If water is present, bleed
tank until water is removed. This water is added to the extract tank.
2. Pump contents of the raffinate tank back up to the feed tank.
3. Check feed composition either in the feed tank (~ 35L) or at the sample point by GC analysis
and adjust the IPA wt% if its too low. If too high, do not adjust.
4. Fill the extractor with Isopar E/IPA feed (if necessary) and bleed air from the feed line. Turn
off the feed flow.
5. Start the mixer and keep agitator speed constant.
6. Open the solvent, feed, extract, and raffinate ball valves; and start the flow of solvent (water)
into the column.
7. If no interface is present between the solvent entrance and the raffinate exit, let the dispersed
phase rise and form the upper interface.
8. When the upper interface forms, (re-)start the feed flow.
9. Control the interface level by adjusting the height of the inverted U on the extract line from
the bottom of the tower.
10. Periodically check the raffinate stream for steady state by gas chromatography.
11. Check the composition of the extract stream by hydrometer. This provides a check on
attainment of steady state, and on the IPA mass balance.

1
These calibrations are the result of student efforts in Spring 2009 (Kirzner and Kaur). Ambient temperature
information for the calibration is not available.

Edited from DBM original by HJT 3 Fall 2011
Operating Notes
1. The extract stream (water + IPA) composition versus specific gravity tables are found in
Perrys Handbook [5, Chapter 2]. Use these data to interpolate weight percent. (Look closely;
there is an error in the Perrys table.)
2. The upper interface level adjustment (inverted U) is sensitive. Movements of a fraction of an
inch are often sufficient.
3. The specific gravity of the feed or raffinate can (and should) be measured by hydrometer.
4. There appears to be a problem with emulsification in the column at low solvent to feed ratios
(ml/min solvent / ml/min feed). Ratios way below 1 may lead to emulsification and even
higher ratios (~1.5) may cause problems at very high agitator speeds (i.e., >1200 rpm). Such
conditions should be avoided unless specifically designated as part of an experimental
program request.
5. Assume that the properties of n-nonane are a good approximation for those of Isopar-E,
especially for equilibrium data purposes. The ternary water/IPA/n-nonane system exhibits
Type I equilibrium behavior at room temperature.
Gas Chromatograph (GC) Operation
The GC is used to separate and quantify the components in a sample. Each component will be
recorded as a separate peak on the integrator/recorder (all the components of Isopar-E will be
combined by the integrator to give the "nonane" result). Each peak's area % is related to the wt %
in the sample. You must calibrate the GC to obtain this relationship using standard calibration
samples, which you will make up yourselves. Typical sample injection volume is between 0.15
and 0.2 L via a dedicated syringe. The elution order is isopropanol and then nonane. The
instructor will supply additional details.
Some Safety Considerations
1. Return all unneeded feed and raffinate sample material to the raffinate storage tank, place the
empty bottles on top of the LLE GC, and put the bottle caps in the drawer. If there are feed or
raffinate samples that you must save till a later time to analyze by GC, cover the cap of these
bottles with Parafilm, place them in a beaker in the laboratory refrigerator. Make sure the
beaker is labeled with your name(s) and the chemical nature of the samples.
2. Return all extract sample material to the extract storage tank.
3. Clean up any spills.
4. Be careful with the hydrometer - it is fragile.
Shutdown Procedure
When leaving for the day, turn off the agitator and main power switch. Close the feed and
solvent ball valves. Leave the raffinate and extract ball valves open.

Edited from DBM original by HJT 4 Fall 2011
Analysis of Solvent Extraction
McCabe-Thiele Method (Solute-Free Basis)

FN = moles/sec of feed diluent, n-nonane, flowing in the column; approximately constant
through the column.
SN = moles/sec of extraction solvent, water, flowing in the column; approximately constant
through the column.
X
f
= moles IPA per mole n-nonane in the feed.
Y
s
= moles IPA per mole water in entering solvent = 0.
Y
e
= moles IPA per mole water in extract stream leaving the column.
X
r
= moles IPA per mole n-nonane in the raffinate stream leaving the column.

At steady state, a material balance on IPA between the feed end of the column and any stage, n
(see dotted outline above) is:
n e 1 n f
X F Y S Y S X F ' + ' = ' + '
+
(3)
Solving for Y
n+1
produces the operating line:
f e n 1 n
X
S
F
Y X
S
F
Y |
.
|

\
|
'
'
+
'
'
=
+
(4)
Since FN and SN are approximately constant through the column, this will be a straight line with
slope FN/SN. It relates the compositions Y
n+1
and X
n
of the two immiscible streams passing one
another at any point in the column. In particular, the equation is satisfied at both ends of the
column, so the points (X
f
, Y
e
) and (X
r
, Y
s
) lie on the line.
Hence, if these two points are determined experimentally, the operating line can be plotted as a
straight line on the X-Y diagram. Use the data in the handout to generate an equation for the
equilibrium curve, and plot it on the same diagram. Then the number of theoretical stages
required for the given separation can be stepped off in the usual McCabe-Thiele procedure. Do
this numerically using Excel.
The Kremser Equation
If the equilibrium line, as well as the operating line, is straight, then the Kremser equation (see
your Unit Operations textbook or Perry's for more detailed information on Solvent Extraction)
can be used to solve for the number of theoretical stages. The equilibrium line must be of the
following form:
Y = mX (5)
Where the slope, m, is constant.
Edited from DBM original by HJT 5 Fall 2011
If the equilibrium line is not straight, but the slope doesn't vary much, the geometric mean of m
at the two ends of the column can be used in the Kremser equation to given an approximate
answer.
The ChemSep Program
A computer program, ChemSep4, which does rigorous stage-to-stage calculations for the
column, is available on the computers in the lab and in rooms 288 and 292. The instructor will
show you how to use the program. ChemSep4 can be used either to: (1) perform stage to stage
calculations assuming equilibrium on the stages; or (2) perform a non-equilibrium (mass
transfer) analysis on the stages, assuming enough information on the column internals can be
supplied to the program. The closest match for an internals option in ChemSep4 to the York-
Scheibel column is the "RDC" (rotating disk contactor) internals option. Use the mixer (paddle)
diameter for "ROTOR" and the column diameter for "STATOR". Your instructor will supply
you with an example file using UNIQUAC properties.
Droplet Diameter and Holdup in Liquid/Liquid Extraction
The mass transfer coefficient(s) and the interfacial area for mass transfer together make up the
resistance or lack thereof to movement of solute from one phase to another. Key
experimental variables can affect either or both of these items for the better or the worse.
In order to determine the effects of the key variables in this experiment on the interfacial area
between the phases, two approaches are possible. One is to find a specific correlation for
interfacial area for a stirred contactor of this type (4-blade paddles). The other is to use separate
correlations for the "holdup" c (volume dispersed phase/total volume) and the "Sauter mean drop
size" d
vs
(the average drop size based on a volume/surface area calculation). The interfacial area
in a stage can be related to these two quantities (derive the relationship).
For holdup, c, many conflicting correlations exist [2]. However, a working model is:
) U exp(B U E A
c
n
d
m
=
(6)
Where A and B are constants which depend on almost all of the standard liquid physical
properties of both phases, U
c
is the superficial continuous and U
d
the superficial dispersed phase
axial velocities, m ~0.75 and n~1.

The quantity E is a fundamental one in all two-phase flow processes, called the energy
dissipation/unit mass. An increase in E always leads to smaller droplet or bubble sizes, and
usually to a higher value of holdup, c. E is given for the case of a two-phase liquid/liquid agitated
dispersion by:
H D
D N 4N
E
2
c
5
R
3
p
=
(7)
where N is the rotor speed, D
R
the rotor diameter, D
c
the column diameter, H the stage or
compartment height, and N
p
the "power number", which is a characteristic function for a given
type of agitator. For turbulent flow, N
p
is roughly a constant. For laminar flow, N
p
is inversely
proportional to N.
For droplet size, almost all correlations, for any agitator type, are of the form [3]:
0.6
R
vs
We K
D
d

=
(8)
Edited from DBM original by HJT 6 Fall 2011
K is (again) a physical property-dependent constant, and We is the characteristic Weber number,
which for this process is:

D N
We
3
R d
2
=
(9)
where o = interfacial tension between phases, and
d
is the density of the dispersed phase.
The Weber number, We, represents the ratio of inertial (kinetic) forces to forces arising from
surface tension; analogous to the Reynolds number, Re, (the ratio of inertial to viscous forces).
From the above equations and the mass transfer coefficient correlations, the effects of such
variables as N, U
d
and U
c
on the mass transfer flux can be derived.
References
1. Taylor, J. A., Uncertainty Analysis,
http://people.clarkson.edu/~taylorja/es223/fall2004/resources/notes/uncertainty.pdf, (Last
accessed 01/13/06).
2. Godfrey et al. Chem. Eng. Prog. Dec. 1989. p. 61.
3. Kumar and Hartland. Ind. Eng. Chem. Res. 34, 3925 (1995).
4. McCabe, W. L., J. C. Smith and P. Harriott. Unit Operations of Chemical Engineering, 7
th

Ed. New York: McGraw-Hill, 2005.
5. Perry, R. H. and D. W. Green, eds. Perrys Chemical Engineers Handbook, 7
th
Ed. New
York: McGraw-Hill, 1997.