CHAPTER

EIGHT
EXTRACTION

8.1

Liquid-Liquid Extraction

8.3

Solid-Liquid Extraction by Soxhlet Apparatus

One of the principal objects of theoretical

research is to find the point of view from
which it can be expressed with greatest
simplicity.
J.W.GIBBS

Chapter 8: EXTRACTION

8.1 LIQUID-LIQUID EXTRACTION

Keywords : Liquid-liquid extraction, mass transfer, organic removal.

8.1.1 Object

The object of the experiment is to demonstrate how a mass balance performed on the extraction
column, and to measure the mass transfer coefficient and its variation with flow rate with the
aqueous phase as the continuous medium.

8.1.2 Theory

Many processes in chemical engineering require the separation of one or more of the
components of a liquid mixture by treating the mixture with an immiscible solvent in which
these components are preferentially soluble. In some cases purification of a liquid may be the
function of the process, in others the extraction of a dissolved component for subsequent
processes may be the important aspect. An example of the former is the preparation of the pure
organic liquids from products of the oil industry. Liquid-liquid extractions may also be used as
energy saving processes by, for example, eliminating distillation stages. It is possible, of course
that the substance of interest may be heat-sensitive anyway and that distillation is accordingly an
unacceptable process.

When separation by distillation is ineffective or very difficult, liquid extraction is one of the
main alternatives to consider. Close-boiling mixtures or substances that cannot withstand the
temperature of the distillation, even under a vacuum, may often be separated from impurities by
extraction, which utilizes chemical differences instead of vapor pressure differences. For
example, penicillin is recovered from fermentation broth by extraction with a solvent such as
butyl acetate. Another example for liquid extraction is recovering acetic acid from dilute
aqueous solutions; distillation would be possible in this case, but the extraction step considerably
reduces the amount of water to be distilled.

When either distillation or extraction may be used, the choice is usually distillation, in spite of
the fact that heating and cooling are needed. In extraction the solvent must be recovered for
reuse (usually by distillation), and the combined operation is more complicated and often more
expensive than ordinary distillation without extraction. However, extraction does offer more
flexibility in choice of operating conditions, since the type and the amount of solvent can be
varied as well as the operating temperature. In many problems, the choice between the methods
should be based on a comparative study of both extraction and distillation.

In liquid-liquid extraction, as in gas absorption and distillation, two phases must be brought into
contact to permit transfer of material and then be separated. Extraction equipment may be
operated batchwise or continuous. The extract is the layer of solvent plus extracted solute and
the raffinate is the layer from which solute has been removed. The extract may be lighter or
heavier than the raffinate, and so the extract may be shown coming from top of the equipment in
some cases and from the bottom in others. The operation may of course be repeated if more than
one contact is required, but when the quantities involved are large and several contacts are
needed, continuous flow becomes economical.

The rate at which a soluble component is transferred from one solvent to another will be
dependent, among other things, on the area of the interface between the two immiscible liquids.
Therefore it is very advantageous for this interface to be formed by droplets and films, the
situation being analogous to that existing in packed distillation columns.

The theory for the system Trichloroethylene-Propionic acid-Water is as follows:

Let

Vw : Water flow rate, lt/s

Vo : Trichloroethylene flow rate, lt/s
X : Propionic acid concentration in the organic phase, kg/lt
Y : Propionic acid concentration in the aqueous phase, kg/lt

Subscripts:

1 : Top of column
2 : Bottom of column

Chapter 8: EXTRACTION

Mass Balance :

Propionic acid extracted from the organic phase (rafinate).

= Vo ( X 1 X 2 )

(8.1.1)

Propionic acid extracted by the aqueous phase (extract)

= Vw ( Y1 0)

(8.1.2)

Therefore theoretically,
Vo ( X 1 X 2 ) = Vw ( Y1 0)

(8.1.3)

Mass transfer coefficient:

MTC =

where

Rateof acid transfer

Volumeof packing Meandriving force

(8.1.4)

Log mean driving force : (X1-X2) / ln (X1/X2)

X1 : Driving force at the top of the column = (X1-X1*)
X2 : Driving force at the bottom of the column = (X2-X2*) = X2

where X1* and X2* are the concentrations in the organic phase which would be in equilibrium
with concentrations Y1 and Y2 ( = 0.0) in the aqueous phase, respectively. The equilibrium
values can be found using the distribution coefficient for the chemicals used (Assumde that
Y=KX relation holds at equilibrium for a constant K). Rate of acid transfer may be calculated
using Eqs.(8.1.1) or (8.1.2) based on raffinate or extract phases, respectively.

8.1.3 Apparatus

The apparatus of this experiment is shown in Figure 8.1.1.

1.) Solvent collection tank, initially empty

6.) Water feed tank, initially full

2.) Solvent feed tank, initially full

7.) Water collection tank, initially empty

3.) Organic solution pump

8.) Extraction column

4.) Water pump

9.) Top and bottom electrodes

5.) Rotameter

Figure 8.1.1 - Liquid-liquid extraction apparatus.

8.1.4 Experimental Procedure

1.

Add 100 ml of propionic acid to 10 liters of trichloroethylene. Mix well to ensure an even
concentration then fill the organic phase feed tank (bottom tank) with the mixture.

2.

Switch the level control to the bottom of the column by keeping the bottom electrodes on.
(switch S2 valve on)

3.

Fill the water feed tank with 15 liters of clean demineralised water, start the water feed
pump and fill the column with water at high flow rate.

4.

As soon as the water is above the top of the packing, reduce the flow rate to 0.2 lt/min.

Chapter 8: EXTRACTION

5.

Start the metering pump and set at a flow rate of 0.2 lt/min.

6.

Run for 15-20 minutes until steady conditions are achieved, monitor flow rates during this
period to ensure that they remain constant.

7.

Take two or three batches of 15 ml samples from the feed, raffinate and extract streams.

8.

Titrate 10 ml of each sample against 0.1 M NaOH using phenolphthalein as the indicator.
(To titrate the feed and raffinate continuous stirring using a magnetic stirrer may be
needed).

9.

Repeat the experiment with water flow rate being increased to 0.3 lt/min.

Note : Calibration of pump is needed whenever a change in flow rates is necessary. The procedure for calibration is
as follows :

The solvent metering pump is calibrated in percentage of maximum flow which varies slightly from pump to pump.
The pump should be calibrated initially by setting F2 to 100%, setting valve V8 to the calibrated position and
measuring the flow from the pump, using a measuring cylinder and stopwatch. Calculate the flow rate produced
settings of 10% intervals (ml/min), then plot a graph of ml/min against percentage of metering pump stroke.
Thereafter any selected flow may be obtained by using the graph.

8.1.5 Report Objectives

1.

Find propionic acid concentrations in each stream. Calculate the average value for each
data point. Check the variances and eliminate the outliers if there are any. Carry out the
following calculations using the refined data set.

2.

Calculate the mass transfer coefficients based on both phases.

3.

What is the maximum possible acid transfer rate? Calculate the column efficiency using
experimental and maximum acid transfer rate. What should be done to achieve the
maximum acid transfer rate?

4.

Repeat the calculations for all flow rates.

5.

Try to answer the following questions in your discussion and conclusion:

a) Why does the mass transfer coefficient depend on the phase selected as the base?
b) How does the flow rate affect MTC? Why?
c) How can the efficiency of the column be increased?
d) Were there any source of error in the experiment? How can this experiment be
improved?

8.1.6 References

1.

Bennett, C. O., and J. E. Myers, Momentum, Heat and Mass Transfer, 3rd edition, McGrawHill, 1983.

2.

Perry, R. H., and D. Green, Perrys Chemical Engineering Handbook, 6th. edition,
McGraw-Hill, 1984.

3.

Sinnott, R. K., J. M. Coulson, and J. F. Richardson, An Introduction to Chemical

Engineering Design, 1st edition, Pergamon Press, 1983.

Chapter 8: EXTRACTION

8.3 SOLID-LIQUID EXTRACTION BY SOXHLET APPARATUS

Keywords : Leaching, solute, solvent, cocurrent, countercurrent, multiple system, triangular

diagram.

8.3.1 Object

The object of the this experiment is to study the basic principles of leaching.

8.3.2 Theory

Extraction is a term used for an operation in which a constituent of a liquid is transferred to

another liquid (solvent). The term solid-liquid extraction is restricted to those situations in which
a solid phase is present and includes those operations frequently referred to as leaching,
lixiviation and washing.

Extraction always involves two steps :

1.

Contact of the solvent with the solid to be treated so as to transfer the soluble constituent
(solute) to the solvent;

2.

Separation or washing of the solution from the residual solid.

These two steps may be conducted in separate equipment or in the same piece of equipment.

Liquid always adheres to the solid which must be washed to prevent either the loss of solution if
the soluble constituent is the desired material or the contamination loss of the solids if these are
the desired material. The complete process also includes the separate recovery of the solute and
solvent. This is done by another operation such as evaporation or distillation.

The equipment used for solid-liquid extraction is classified according to the manner in which the
first step is done. The term solid bed or fixed bed refers to any operation in which the solid
particles are kept in relatively fixed positions with respect to each other while the solvent flows

through the bed of solid particles, whether or not the bed of solid material remains stationary
with respect to the earth during the extraction. The opposite of this situation, called dispersed
contact, refers to any operation in which the solid particles, suspended in the fluid, are in motion
relative to each other and to the solvent during the time of contact.

Solid-liquid extraction

Solid-liquid extraction (leaching) is the process of removing a solute or solutes from a solid by
using of liquid solvent. Leaching is widely used in chemical industries where mechanical and
thermal methods of separations are not possible or practical. Extraction of sugar from sugar
beets, oil from oil bearing seeds, production of a concentrated solution of a valuable solid
material are typical industrial examples of leaching. Leaching process can be considered in three
parts :

1.

Diffusion of the solvent through the pores of the solid

2.

Solute dissolves in the solvent.

3.

Transfer of the solution from porous solid to the main bulk of the solution.

In fixed-bed contacting the solid particles are stationary in a tank, in which the solvent is
allowed to percolate through the bed of undissolved solids. In leaching by the soxhlet apparatus
multiple contact of solids with the fresh solvent is performed at each stage of operation. This
equivalent to multiple cocurrent system, as described in the following diagram.

fresh solvent

solid
underflow

solid
feed
solution overflow

Figure 8.3.1 - Multiple cocurrent system.

Chapter 8: EXTRACTION

8.3.3 Apparatus

The apparatus used in this experiment is shown in Figure 8.3.2

1.) Water inlet

2.) Soxhlet condenser
3.) Water Outlet
4.) Soxhlet extractor (lower d = 1.5
cm, upper d = 4.3 cm)
5.) Round bottom flask (1000 ml)
6.) Electrical heater

Figure 8.3.2 - Soxhlet apparatus.

8.3.4 Experimental Procedure

1.

Weigh an amount of oil containing ground seeds.

2.

Dry them in for 30 minutes in an oven @ 105 C and determine the moisture content.

3.

Put ends of the samples into the thimble and place it into the extractor of the soxhlet

apparatus. Pour 300 ml hexane into the pot as a solvent. Start leaching and continue the
process up to the end of the third siphon.

4.

Take the solid in the thimble and put it into the glass container closing the lid so that no
solvent is lost by evaporation. Weigh the sample. Dry it into the oven and reweigh.

5.

Take a liquid sample from the extract. Determine the oil contents of the liquid sample using
refractometer.

6.

Distill the extract in order to separate the oil and solvent.

8.3.5 Report Objectives

1.

Perform the necessary mass balance.

2.

Calculate the yield of extractor and percent oil recovery.

3.

Analyze the operation on a triangular diagram.

8.3.6 References

1.

Brown, G. G., Unit Operations, John Wiley & Sons ,1956.

2.

McCabe, W. L., and J. C. Smith, Unit Operations of Chemical Engineering, McGraw-Hill,

1956.

3.

Perry, R. H., and D. Green, Perrys Chemical Engineers Handbook, 6th Edition, McGrawHill, 1988.