Instruction Manual

CE 620 Liquid-Liquid
Extraction Unit
 CE620 Liquid- Liquid Extraction
09/01
All rights reserved G.U.N.T. Gerätebau GmbH, Barsbüttel, Germany

Instruction Manual

Please read and follow the instructions before the first installation!

Publication-No.: 918.000 00 D 620 12 09/01

 CE620 Liquid- Liquid Extraction

Table of Contents
1 Introduction . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1

2 Unit description . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 2

2.1 Unit layout . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 2

2.2 Extraction column . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 3
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2.3 Distillation unit . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 4

2.4 Feed and solvent controls . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 5
2.5 Control cabinet . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 5
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2.6 Feed pump and solvent pump . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 7

2.7 Process flow diagram . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 8
2.8 Notes on commissioning and operation. . . . . . . . . . . . . . . . . . . . . . . 8

3 Safety Instructions. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 11

3.1 Hazards to life and limb . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 11

3.2 Dangers to the unit and its functionality . . . . . . . . . . . . . . . . . . . . . . 11

4 Theoretical Principles . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 13

4.1 Liquid liquid extraction . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 13

4.1.1 Basic Principles . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 13
4.1.2 Solvent extraction in cross-flow and counter-flow senses . . 19
4.1.3 Requirements of feedback components
and the solvent for extraction . . . . . . . . . . . . . . . . . . . . . . . 23
4.2 Distillation . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 24
4.2.1 Basics of distillation . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 24
4.2.2 Structure of a distillation unit . . . . . . . . . . . . . . . . . . . . . . . . 29
 CE620 Liquid- Liquid Extraction

5 Experiments . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 30

5.1 Preparation for the experiment . . . . . . . . . . . . . . . . . . . . . . . . . . . . 30

5.2 Performing the experiment . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 30
5.3 Evaluation of the experiment . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 31
5.4 Performing an experiment with benzene - benzoic acid - dist. water . . . 32

6 Appendix . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 34

6.1 Technical Data . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 34

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6.2 Calibration curve water- benzoic acid . . . . . . . . . . . . . . . . . . . . . . . 35

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 CE620 Liquid- Liquid Extraction

1 Introduction

For liquid mixtures which can’t be separated

or can only be inadequately separated by me-
chanical or thermal techniques it is possible to use
physical chemical separation techniques . These
are: solids extraction, ion exchange purification
and liquid-liquid extraction.
The laboratory equipment CE620 liquid-liquid ex-
traction equipment can separate liquid mixtures by
liquid-liquid extraction .
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The laboratory equipment is not limited to any particular

multi-component mixture, it can deal with a wide
variety of liquids . The analytical equipment for
multi-component systems must be provided by the
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user .
The unit can be used for training in the areas of thermal
processing and the field of apparatus construction.

The range of experiments covers the following areas:

- Liquid-liquid extraction with various
multi-component systems
- Observation of the extraction process

The unit is designed to allow the extraction process

to be observed. In the experimental unit is included
a distillation device for reprocessing the solvent.
The system is intended only for educational purposes
and not for industrial production.

1 Introduction 1
 CE620 Liquid- Liquid Extraction

2 Unit description

2.1 Unit layout

3
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4 5
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1
7

14

13
12 11 10 9

1. Extraction column 8. Reserve feed vessel

2. Distillation unit 9. Feed pump
3. Extract vessel 10. Solvent pump
4. Feed and solvent controls 11. Solvent vessel
5. Control cabinet for pump operation and heater controls 12. Overpressure valves for pumps
6. Distillate vessel 13. Regulating valve for phase interface
7. Feed vessel 14. Welded frame with castors

2 Unit description 2
 CE620 Liquid- Liquid Extraction

The unit is designed as a transportable experimental

unit for a variety of experimental mixtures. The
extraction column, liquid vessel and distillation unit
are arranged to be clearly seen in the unit. The
transport of liquids is performed by two pumps,
which are connected to the individual components
using VITON hoses. The pump controls and the
distillation heater controls are mounted in the
control cabinet. The volumetric flow of feed and
solvent can each be regulated by plug displacement
flow indicators. There are two three-way valves
which permit both the feed flow and solvent flow to
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be changed over between continuous and batch

operation. Operation of the distillation unit requires
an external water supply. This can be connected
to the distillation head using the hoses supplied.
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The liquid vessels are each equipped with a liquid

level indicator and shut-off valve.

2.2 Extraction column

The extraction column comprises a glass tube of

DURAN glass. It has a diameter of 50mm. The
glass cylinder is filled with soda glass Raschig
rings. The column packing is so arranged that
there is clear space within the column above and
below it. In these clear spaces the operation of the
phase interfaces can be observed. The glass cy-
linder is capped with stainless steelcovers, which
carry the connections for the liquids distribu-
tion and liquids removal. The main function of the
column is the complete mixing of feed and solvent.

2 Unit description 3
 CE620 Liquid- Liquid Extraction

2.3 Distillation unit

The distillation unit comprises a 5 ltr capacity

5 destillation receiver (1) with a Hempel type packed
column (2) and a distillation tube (3) with a
6 Liebig condenser. The packed column is filled
with Raschig rings . The round-bottomed flask
3 is heated by a hemispherical heater (4), which
is controlled by an industrial type PID control-
10 ler in the control cabinet.
The bottoms temperature in the destillation receiver
is measured by a PT 100 measuring sensor.
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2
The distillation unit distils solvent from the extract.
The electrical functions are limited to control of the
8 7 bottoms temperature.
The head temperature can be read off on an analogue
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1
head thermometer (5).
4 For distillation, an external water supply is required
to the connections (6) on the distillation tube
The distillation unit is freely supported with in the
9
frame by clamps.
Fig. 2.1 Distillation unit The distillation unit is filled by means of a feed tube (7)
with shut-off valve. The destillation receiver can be
cleaned by using a side neck (8) which is plugged
in normal operation.
To drain the bottom product a drain valve (9) with
ball valve is attached to the destillation receiver .
The distillation unit has also a water jet pump, with
which the distillation unit can be evacuated though
a connection (10) on the distillation tube.

Fig. 2.2 Destillation receiver with

PT100 and feed pipe with
shut-off valve

2 Unit description 4
 CE620 Liquid- Liquid Extraction

2.4 Feed and solvent controls

The controls comprise two volumetric quantity

meters and two three-way valves. The quantity
meters permit exact adjustment of the volumetric
flow of feed and solvent. They are plug displacement
flow indicators, which are chemical-resistant. The
three-way valves permit both the feed flow and
solvent flow to be changed over between
continuous a n d batch operation. In batch
operation the feed and solvent are fed from the
respective storage tanks, through the extraction
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column, then back to the storage tanks . In

continuous operation the feed and solvent are fed
from the respective storage tanks, through the
extraction column, then into the receiver vessels.
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The feed flow is fed into the reserve feed vessel,

Fig. 2.3 Feed and solvent controls
and the solvent flow into the extract vessel. For
continuous operation the three-way valves are set
as shown in figure 2.4.
In the controls the hose connections between
the volumetric quantity flow indicators for the
extraction column and the column and the three-way
valves are fitted with colour-coded quick release
couplings.
This enables the equipment to be operated even
with very different multi-component mixtures, in
which the solvent may have specific gravity greater
or lesser than the feed mixture. The variants are
set out is the table below. In variant 1 the density of
the solvent is greater than that of the feed. In
variant 2 it is the other way round.
Fig. 2.4 Valve settings for
continuous operation

Variant Volumetric quantity Volumetric quantity Three-way valve/ Three-way valve/

meter/ hose (feed) meter/ hose hose (feed) hose (solvent)
(solvent)
1 Red / Red Blue / Blue Yellow / Yellow Green / Green
2 Red / Blue Blue / Red Yellow / Green Green / Yellow

2 Unit description 5
 CE620 Liquid- Liquid Extraction

2.5 Control cabinet

3

Temperature Controll

2
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Destillationsheat er Feedpump Solventpump

4
1 1 1 1

0 0 0
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7 6 5
1. On / off switch for distillation heater
The control cabinet contains the on / off switches
2. PID controller for bottoms temperature
for the distillation heater, the solvent pump and
3. Signal lamps for operation
feed pump, together with the PID controllers
4. On / off switch for solvent pump f o r controlling the bottoms temperature. The
5. EMERGENCY STOP button actual temperature is sensor by a PT 100 thermo-
6. On / off switch for feed pump meter and is shown on the controller . The set
7. Master Switch temperature can be selected by the operating
keys.
The control cabinet also contains the mainswitch and
an EMERGENCY STOP button. A key is provided
for opening the control cabinet W ith in the control
cabinet there are t h e motor protectionswitches
for the pumps and the safety controllers for the
distillation heater and the overall unit.

2 Unit description 6
 CE620 Liquid- Liquid Extraction

2.6 Feed pump and solvent pump

The feed pump is a gear pump with a flange-mounted

electric motor. This motor is a single phase AC
motor. The speed of the motor is fixed at 3000 rpm.
On the head of the pump there is an overpressure
valve which opens at a settable overpressure. This
pump can convey low viscosity liquid mixtures. The
type of this pump has been selected as being of
materials with good chemical resistance. The bea-
rings of the gear pump have no contact with the
material being conveyed, so that lubrication by the
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Fig. 2.5 Feed pump material being conveyed is not necessary.

The solvent pump is a diaphragm dosing pump
with a single phase AC flange-mounted electric
motor. The pump runs at a fixed speed. A knob on
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the side allows the piston stroke of the pump to be

adjusted. The setting can be read on a scale on
the pump head. This allows the dosing quantity per
stroke to be set. The factory setting of the piston
stroke is 100%
Since the pumps are positive displacement pumps ,
on the pressure side of each pump there are over-
pressure release valves fitted. The valves open in
Fig. 2.6 Solvent pump the event of overpressure and allow the feed /
solvent to flow into the respective storage tank.
The overpressure valves must be set to match
one another. The matching must be performed
a new for each multi-component mixture.

Fig. 2.7 Overpressure valves for sol-

vent and feed

2 Unit description 7
 CE620 Liquid- Liquid Extraction

2.7 Process flow diagram

21
6

16
T1

1
7 2
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5
13 14
15 T2

3 4
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20

22 19
12 23

9 10 11
17

18

1. Extraction column 13. Quick-release coupling (red)

2. Distillation unit 14. Quick-release coupling (blue)
3. Volumetric feed quantity meter 15. Quick-release coupling (green)
4. Volumetric solvent quantity meter 16. Quick-release coupling (yellow)
5. Solvent three-way valve 17. Solvent pump
6. Feed three-way valve 18. Feed pump
7. Extract vessel 19. Overpressure valve for solvent
8. Distillate vessel 20. Overpressure valve for feed
9. Solvent storage tank 21. Manipulation Valve
10. Feed storage tank 22. Drain valve (1)
11. Reserve feed vessel 23. Drain valve (2)
12. Regulating valve for phase interface

2 Unit description 8
 CE620 Liquid- Liquid Extraction

2.8 Notes on commissioning and operation

- The column is filled by means of the feed pump

and solvent pump. The initial feedmixture is
prepared outside the unit and poured into the
feed storage tank. The same applies to the
solvent.
- Close the regulating valve for the phase interface
and using the feed pump fill the extraction
column with the feed mixture . Allow the feed
mixture to flow continuously in a circuit.
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- Switch on the solvent pump and feed solvent

into the extraction column.
- Open the regulating valve when a clear
phase interface can be seen in the free spaces
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of the extraction column. By regulating the

feed flow and solvent flow, using the volumetric
quantity meters and the regulating valve,
maintain the phase interface at a constant height.

- In batch operation, allow the feed and solvent

to flow in a circuit and at regular intervals take
samples from the solvent and feed vessels, for
analysis of the composition. When the desired
separation has been achieved, divert the feed flow
into the reserve feed vessel and the solvent flow
into the extract vessel.
- In continuous operation the feed and solvent
are fed directly from the storage tanks,
through the extraction column, then into the
receiver vessels.
- Where the feed mixture has a density
significantly less than that of the solvent,
the height of the liquid column of feed
mixture in the extraction column may be
insufficient to convey the solvent into
the extraction vessel. In this case the flow
resistance at the head of the extraction co-

2 Unit description 9
 CE620 Liquid- Liquid Extraction

lumn must be increased, by using the manipu-

lation valve (21).
- For emptying the unit it is necessary t o p u m p
the feed from the feed vessel into the
reserve feed vessel. The liquid can be drained
from the reserve feed vessel, using the drain
valve. For the solvent, which as a rule must be
reprocessed, the liquid can be drained either
from the extract vessel or the distillate vessel.
- To drain the extraction column open the drain
valves (1) & (2) and let the liquid run off into
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a suitable container. Run solvent- and

feedpump as long as air is running through the
flow-meters obviously.
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- After emptying, the unit should be washed

through several times with distilled water ( run
the water into suitable containers and arran-
ge for it to be correctly disposed of ).
- For distillation it is necessary that the boiling
temperature of the component to be distilled
is known and is entered into the PID controller
using the arrow keys. Then the rotary switch is
used to set the distillation heater.
- For vacuum distillation the water jet pump
supplied should be connected to a suitable
water supply and using the hose provided a
vacuum connection made between the
distillation tube and the water jet pump.

2 Unit description 10
 CE620 Liquid- Liquid Extraction

3 Safety Instructions

The experimental instructions, in particular the safety instructions, are

to be read through carefully prior to commissioning the unit.
Prior to starting the experiments, the participants are to be briefed on the safety
aspects and the correct use of the unit.

3.1 Hazards to life and limb

RISK of electric shock!

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- Only technically qualified personnel may

open the control cabinet or work on the electri-
cal equipment
- Prior to opening the control cabinet and
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working on the electrical system, unplug

them from the mains!
- Protect the electrical equipment from water and
humidity.

DANGER of burns!
- Do not touch the hemispherical heater and
glass components of the distillation unit whilst
distillation is in progress.
- When emptying the distillation receiver be
sure to pour hot bottom product into suitable
containers. Wear protective gloves at all times.

DANGER, health risk!

- When handling the chemicals that are used, work
strictly to the hazard instructions and safety
instructions described in the safety data sheets.
This applies particularly when filling and emp-
tying the unit.

3 Safety Instructions 11
 CE620 Liquid- Liquid Extraction

3.2 Dangers to the unit and its functionality

ATTENTION!
- The unit is designed exclusively for use with the
material combination benzene, benzoic acid
and distilled water.If used with other material
combinations, make sure it is resistant to the
materials used. Only use chemicals that do not
cause damage to VITON, PVDF, PTFE and
1.4035.
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ATTENTION!
- Never heat the distillation round-bottomed flask
when it is empty! There is a risk of overheating,
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which can lead to embrittlement and

consequent failure of the heater.

ATTENTION!
- The hemispherical heater is not protected
against humidity. Take care therefore not to
expose it to humidity or wetting, nor to aggressive
media. If the heater does become wet, it must be
fully dried out (preferably in a drying cupboard)
before being used again.

3 Safety Instructions 12
 CE620 Liquid- Liquid Extraction

4 Theoretical Principles

4.1 Liquid liquid extraction

4.1.1 Basic Principles

Liquid-liquid extraction, also known as Solvent

extraction, is an important thermal separation
technique supplementary to distillation and
rectification. The separation principle of rectification
is based on separation of a mixture using the
differential boiling temperatures of the component
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liquids , whereas solvent extraction relies on a

suitable solvent called component B to separate
a mixture according to the chemical characteristics
of the components . In contrast to rectification
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( materials transfer between liquid and vapour

phases ) the materials transfer in solvent extraction
takes place between two liquid phases. The most
important pre-requisite for solvent extraction is the
immiscibility of solvent and raffinate.
Solvent extraction has achieved particular importance
for the following applications:
- Solvent extraction can separate a mixture by
their chemical characteristics.
- Solvent extraction can separate a mixture whose
equilibrium curve is near to the diagonal, or
whose equilibrium curve crosses the diagonal.
- If water is present in large amounts in the
mixture that is to be separated, then on energy
consumption grounds, solvent extraction can
be very much preferable to rectification.

4 Theoretical Principles 13
 CE620 Liquid- Liquid Extraction

In the simplest case of the solvent extraction

separation process there are three components
involved:
- component A as the component carried over
- component B as solvent
- component C as the raffinate component

In figure 4.1 the principles of solvent extraction

are shown with the main terms and designations. In
mixture vessel (1) the starting mixture, comprising
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components A + C, and solvent B are mixed using

a mixer (2). A quasi-homogenous mixture of
three components is formed in the vessel ,
which is conveyed to the settling vessel (4) by the
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pump (3) . In the settling vessel the two liquid

phases separate out due to the difference in their
densities. The diagram shows the extraction-
process as an idealised separation process. Only
component A and not component C is taken up in
the solvent phase. No solvent is taken up in the
raffinate phase.

initial mixture, solvent,

Feed F (A + C ) Solvent B
Solvent phase S
( B + part 2 of A )

Phase interface

Raffinate phase R
quasi-homogeneous
(C + part 1 of A )

Fig. 4.1 Principles of solvent extraction or liquid-liquid extraction

4 Theoretical Principles 14
 CE620 Liquid- Liquid Extraction

The distribution of the transfer component A in the

two immiscible liquid phases, the solvent phase S
and the raffinate phase R, is described by
NERNST’s Distribution Law:
cAS
K=
cAR
K= NERNST’s Distribution Coefficient
cAS= Molecular quantity of component A in the solvent
phase
cAR= Molecular quantity of component A in the
raffinate phase
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NERNST’s Distribution coefficient is temperature-

dependant, but in dilute solutions it can be regarded
as constant.
The solvent extraction process can be represented
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and tracked using a triangular diagram and a

loading diagram.
In diagram 4.2 the most important ternary system (also
called a closed loop system) is depicted schematically.
The bi-nodal curve (1) divides the homogeneous
zone (I) from the critical heterogeneous zone (II).
In the heterogeneous zone the three components A,
B and C form two phases, which are in equilibrium.
The concentrations in the two phases at each
point can be found on the bi-nodal curve. The

Fig. 4.2 Triangle diagram and loading diagram for a ternary system.

4 Theoretical Principles 15
 CE620 Liquid- Liquid Extraction

lines linking pairs of equivalence points are

called co-nodes (2). The two phases that are in
equilibrium are termed conjugated phases . The
diagram can be constructed in molecular
proportions or in mass proportions . The corners
of the triangular diagram represent 100% of each
respective component , and the sides of the triangle
represent the composition of a two-component
system . A mixture within the triangular diagram
comprises all three components, with their
concentrations given by the parallels from each of
the respective sides. The molecular quantities or
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mass quantities of each phase are given by the rule

of lever relationship.
The system represented in figure 4.2 is charac-
terised by low solubilities of B in the raffinate
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phase R, and of C in the solvent phase S, and

that these solubilities increase as the proportion
of A increases .
The translation of the bi-nodal curve into the
equilibrium curve (3) in Cartesian co-ordinates
is achieved by translating the end points of the
co-nodes ( e.g. the uppermost co-node in diagram
4.2, designated by a and b ). The critical point KR
is defined as the point where the solvent phase S
and raffinate phase R coincide ( the length of the
co-node at point KR = 0 ). The concentrations are
thus equal and the equilibrium line cuts the 45 °
line.
The three component mixture corresponding to
point P1 in the heterogeneous zone vanishes into
the two liquid phases S1 and R1. The respective
molecular quantities or mass quantities of the indi-
vidual phases can be calculated using thr rule
of lever relationship. They are in inverse pro-
portion to the bands in the diagram.
For the molecular quantities, the following applies:
_____
n R1
= ____
P1S_1
n S1
P1R1

4 Theoretical Principles 16
 CE620 Liquid- Liquid Extraction

For mass quantities, the formula is analogous to

that for molecular quantities.
An example of a closed loop three component system
corresponding to diagram 4.2 is the system pro-
panoic acid (A) - toluene (B) - water (C). From this
system a loading diagram for the process
calculation can be developed.
In the loading diagram (figure 4.3) the solvent
process can be tracked particularly easily. The most
important process parameters can be quickly and
clearly determined.
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In figure 4.3 the equilibrium table and the resulting

loading diagram for the above three component
system are shown. In the equilibrium table,
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columns 1 and 2 show the mass quantities in the

solvent phase. Columns 3 and 4 show the mass
1 2 3 4 5 6 7 8

W AS

VAR
Fig. 4.3 Equilibrium table and loading diagram for propanoic
acid - toluene - water

4 Theoretical Principles 17
 CE620 Liquid- Liquid Extraction

quantities in the raffinatephase. In columns 5

and 6 the mass loading proportions in the
solvent phase and in raffinate phase are shown.
These are determined for instance in row 5 for the
solvent phase as follows:
wAS = 0.147 kg A/ kg S
W AS = 0.147/ 0.853 kg A/ kg B = 0.172 kg A/kg B

For the raffinate phase, it is:

vAR = 0.168 kg A/ kg R
VAR = 0.168/0.832 kg A/kg C = 0.202 kg A/ kg C
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From the mass loading proportions and the

molecular weights are obtained the molecular
proportions in the solvent and raffinate phases.
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For the solvent phase it is:

YAS= 0.172x92/74 kmol A/ kmol B
YAS= 0.214 kmol A/kmol B
For the raffinate phase, it is:
XAR= 0.202x18/74 kmol A /kmol C
XAR= 0.049 kmol A/ kmol C

4 Theoretical Principles 18
 CE620 Liquid- Liquid Extraction

4.1.2 Solvent extraction in cross-flow and counter-flow senses

The process of liquid-liquid separation i s

performed under cross flow, especially for
continuous large flows of materials, or under co-
unter flow, to minimise the quantities of solvent
required.
Cross flow processing (figure 4.4) is characterised
by fresh solvent B being introduced at each
stage. The solvent phase loaded is removed at
each process stage, and as a rule reprocessed in
a rectification stage. The raffinate phase from the
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first stage is renewed in the second stage by

application of fresh solvent. This process can be
seen in schematic representation in figure 4.4 .
In the diagram are depicted theoretical separation
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stages in which the materials flows leaving the

Fig. 4.4 Cross flow process

4 Theoretical Principles 19
 CE620 Liquid- Liquid Extraction

respective separation stage have achieved their

equilibrium. Their concentrations are thus equilibrium
concentrations and therefore co-ordinates
o f a p o i n t o n t h e equilibrium curve in the
loading diagram.

In the counter flow process (figure 4.5) the solvent

and raffinate phases are fed against each other, so
that the incoming fresh solvent flow will extract
further A from the raffinate flow that already is
largely free of A, until the final purity is achieved.
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All rights reserved G.U.N.T. Gerätebau GmbH, Barsbüttel, Germany

Fig. 4.5 Counter flow process

4 Theoretical Principles 20
 CE620 Liquid- Liquid Extraction

The loading diagram allows the concentrations of

the materials flows leaving each theoretical stage
to be easily determined.
The mass balances not only for each indivi-
dual theoretical stage, but also for the overall
process, lead to the following equations.
Balance from stage 1:
. . . . . . . .
m C VAF + m B WAS2 = mC VAR1 + mB WAS1

Balance for the overall process:

. . . . . . . .
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mC VAF + mB WASα = mC VAR3 + mB WAS1

From the above equations it follows that:

.
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mC WAS1 − WAS2 WAS1 − WASα

tanϕ = . = =
mB VAF − VAR1 VAF − VAR3
For any section across the extraction column and
its lower part t h e b a l a n c e f o r t h e trans-
fercomponent A gives the equation for the wor-
king linear relationships:

. . . . . . . .
m C VAR + m B WASα = mC VAR3 + mB WAS

. .
mC . mC .
WAS = . VAR − . VARω
mB mB
( WASα = 0 ; VAR3 = VARω )

The working linear relationships permit that in

the cross-section of the extraction column the
concentration of a phase can be determined, if
the concentration of the other phase is known.

The maximum angle ϕmax achievable with the

same data for the incoming feed flow and for the
final purity of the raffinate flow, if the process is

4 Theoretical Principles 21
 CE620 Liquid- Liquid Extraction

performed with the minimum solvent flow ( com-

pare dotted working line in figure 4.5). Theoreti-
cally, with the application of the minimum solvent
flow the number of stages is unlimited.
In practice the solvent flow actually required,
as against the minimum solvent flow, is set to:
. . .
m B ≈ 1,3 m Bmin
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4 Theoretical Principles 22
 CE620 Liquid- Liquid Extraction

4.1.3 Requirements of feedback components and the solvent for extraction

The tables depicted above contain only possible

examples for three component systems for
liquid-liquid extraction.
An important role in three component systems
is played by the solvent. The most important
requirements for the solvent are:
- The solvent B must be capable of forming a
phase with the component carried over, A. At
this point the densities of the separated phase R
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and the taken up phase S must be separated

as widely as possible.
- The solvent B should contain as much as
possible of A and as nearly as possible an
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absence of C, so that it has a large capacity

whilst at the same time having large selectivity
. The heterogeneous zone should be as
large as possible. An optimum ternary mixture
has been attained when the bi-nodal curve
follows the triangle sides AB and AC.
- The boundary interface surface tension between
the two phases should be as large as possible.
The greater the boundary interface surface
tension, the more energy is required to disperse
one liquid in the other, and the more quickly the
phase separation will proceed.
- No emulsions must form within the extraction
apparatus. The substances must not decompose.
- The viscosity should be low, so that the phases
can easily be mixed, agitated and conveyed.
- Health and safety aspects must be considered
- The boiling temperatures of components A and
B ( which should not form a constant boiling
mixture ) should be widely different, so that
solvent B can be regenerated with as little
work as possible and can be re-used.

4 Theoretical Principles 23
 CE620 Liquid- Liquid Extraction

4.2 Distillation

In this laboratory equipment, two important processes

for materials separation are used. Since the main
purpose of this equipment however is for for field
of solvent extraction, the description of the
theoretical basis for distillation is restricted to the
bare essentials. Further information can be found
in the available technical literature.

4.2.1 Basics of distillation

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The important thermal processes of distillation and

rectification permit one or more of the volatile
components to be recovered at high purity from a
mixture with several volatile components. This
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separation process functions by means of the basic

operations of evaporation and condensation.
The difference between distillation/ rectification
and the separation process of evaporation is that
in evaporation only one of the components is
volatile. In distillation / rectification the vapour
phase has a different composition to the liquid
phase. This fact is the basis for distillation and
rectification.
The difference between rectification and
distillation is that in rectification the vapours
emanating from the recovered condensate are
partially returned to the column and made to
perform materials transfer with the rising vapours
on or at suitable column fitments. In distillation
the rising vapoursare condensed in a condenser
and drawn off.
The relationship between the concentrations in the
vapour phase (y) and the liquid phase (x) can be
calculated for the ideal case using RAOULT’s Law
and DALTON’s Law, if the vapour pressure
curves of the respective components are known.
Normally however the molecular proportions of the
two phases at equilibrium are determined
experimentally. The calculation of the molecular

4 Theoretical Principles 24
 CE620 Liquid- Liquid Extraction

proportions should for instance result in an ideal

two part mixture benzene (A) / toluene (B). An
ideal two part mixture has been achieved
when the partial vapour pressure curves are
linear and the molecules of the components
behave exactly as the pure components on
their own. By RAOULT’s Law:
pA = P0A xA and pB = p0B xB
( when xA + xB = 1 and pA + pB = p )
and DALTON’s Law:
pA = yA p and pB = yB p
09/01

( when yA + yB = 1 and pA + pB = p )
the pressure diagram shown in figure 4.6 can be
created. The pressure diagram shows that the two
part mixture of benzene / toluene behaves ideally
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based on the straight line partial pressure curves (

1 + 2 ). Curve 3 shows the total vapour pressure
by molecular proportion xA.
Diagram 4.7 shows the typical course of the boiling
and condensation lines in the boiling diagram for
benzene / toluene at a pressure of p= 1,01 x105
Pa. From the boiling diagram, as shown in the
diagram, an equilibrium diagram can be created.

Fig. 4.6 Pressure diagram

benzene / toluene

4 Theoretical Principles 25
 CE620 Liquid- Liquid Extraction

The quantitative determination of the equilibrium

condition is determined as follows:

vapour phase
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liquid phase
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Fig. 4.7 Boiling diagram / equilibrium diagram benzene / toluene

4 Theoretical Principles 26
 CE620 Liquid- Liquid Extraction

αxA
yA =
.
1 + x A (α − 1)

For this, α is defined as relative volatility. This is

the relation between the molecular proportions at
equilibrium of the vapour phase and of the liquid
phase.
yA ⁄ xA
α =
yB ⁄ xB
09/01

For an ideal two part mixture by using RAOULT’s

Law and DALTON’ Law it gives:
All rights reserved G.U.N.T. Gerätebau GmbH, Barsbüttel, Germany

Fig. 4.8
Boiling diagram / equilibrium diagram for real mixtures

4 Theoretical Principles 27
 CE620 Liquid- Liquid Extraction

p 0A
α =
p
0B

The greater the numeric value of α , the further the

equilibrium curve lies from the diagonal and
thus the easier is it to achieve separation by
distillation.
In diagram 4.8 for instance boiling diagrams and
equilibrium diagrams for non-ideal two part
mixtures are shown. Further information on these
09/01

mixtures and the quantitative determination of

equilibrium conditions can be found in technical
literature.
All rights reserved G.U.N.T. Gerätebau GmbH, Barsbüttel, Germany

4 Theoretical Principles 28
 CE620 Liquid- Liquid Extraction

4.2.2 Structure of a distillation unit

A distillation unit comprises three main assemblies:

- the distillation vessel for heating the initial
mixture and for collecting the high boiling point
components.
- the reflux condenser for separating the high
boiling point components from the vapour
mixture
- the condenser for condensing the low boiling
point components.
09/01

T1 The most important measured values in a distillation

unit are the boiling temperature in the distillation
vessel and the vapour temperature after the
All rights reserved G.U.N.T. Gerätebau GmbH, Barsbüttel, Germany

reflux condenser. These temperatures give

Condenser information about the concentration of low
boiling point component in the vapour and
concentration of high boiling point component in
the vessel. In figure 4.9 is shown a distillations
Reflux condenser unit in schematic stages.
The reflux condenser is provided here by a packed
column (full bodycolumn). As an alternative to a
T2
packed column, a solid base column or a water-
cooled reflux condenser can be used. In that
case a cooling coil is run through the column, on
which the high boiling point components can
condense. The temperature of the water entering
this cooling coil must however be higher than for a
condenser.
Distillation vessel

Fig. 4.9

4 Theoretical Principles 29
 CE620 Liquid- Liquid Extraction

5 Experiments

The laboratory equipment CE620 contains only the

apparatusrequired for experiments in solvent
extraction. The parts dealing with the analytical
investigation of the test mixtures must be provided
by the user . For this reason the description
o f p r e p a r a t i o n f o r e x p e r i m e n t s , carrying
them outand evaluating them is limited to general
information.
In an extra chapter, the carrying out of an experiment
09/01

with a test mixture of benzene benzoic acid distilled

water is described qualitatively.

5.1 Preparation for the experiment

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Preparation for carrying out the experiment includes:

- Production of the feed mixture, taking account of
safety data sheet information for each component
- Modification of the feed and solvent flows in the
equipment in accordance with chapter 2.4
- Cleaning the extraction equipment after
previous experiments
The experiment should be estimated as requiring
a very large amount of time, since the actual
experiment can commence only once preparation
of the solvent has been completed.

5.2 Performing the experiment

The experiment can be considered in twoparts :

1. solvent extraction
2. reprocessing of the solvent by means
of distillation

Solvent extraction is performed according to the

information set out in chapter 2.8 for commissioning
the equipment. Depending on the method of
operating the equipment, samples taken from the

5 Experiments 30
 CE620 Liquid- Liquid Extraction

solvent storage tankand its composition are

quantitatively determined. When the desired
composition has been achieved, the solvent must
be fed into the extraction vessel, to be processed
further.
If the solvent has reached its maximum
take-up capacityfor one of the components, either
fresh solvent must be added or the solvent in the
equipment must first be reprocessed.
Solvent extraction performance depends on the
operating parameters set out above.
09/01

The second part of the experiment includes

reprocessing the solvent.
For this, the exact composition of the solvent must
be known, so as to determine the exact boiling
All rights reserved G.U.N.T. Gerätebau GmbH, Barsbüttel, Germany

temperature.
This temperature should be entered into PID controller
and monitored at the top thermometer.
The distillate is conveyed into the distillate vessel
and can there be first tested for its purity, before
being fed into the solvent storage tank.
The experiment is complete when the initial
components have been separated into individual
components.

5.3 Evaluation of the experiment

The qualitative and quantitative evaluation of the

experiment depends primarily on the facilities
for analysis and on the data regarding the
experimental mixture. For this reason no attempt is
made at a quantitative evaluation of the experiment.

5 Experiments 31
 CE620 Liquid- Liquid Extraction

5.4 Performing an experiment with benzene - benzoic acid - dist. water

This chapter describes the performance of an

experiment with a test mixture of benzene - benzoic
acid - dist. water. The objective is to separate out the
benzoic acid from the benzene - benzoic acid feed
mixture, using distilled water.
In order to measure the concentration of benzoic
acid in the water, the electrical conductivity can be
measured directly, to indicate the concentration.
With this experimental mixture, no quantitative
evaluation is undertaken, instead a qualitative de-
09/01

termination of the transfer of benzoic acid from the

benzene into the water .
The conductivity of the water can be measured using
the "Watercheck" pH and conductivity
All rights reserved G.U.N.T. Gerätebau GmbH, Barsbüttel, Germany

meter supplied .
The concentration of benzoic acid in the benzene
cannot be measured directly. For this, a defined
quantity of benzene must be mixed with a defined
quantity of dist. water. After being thoroughly
mixed, the electrical conductivity of the water
indirectly indicates the concentration of benzene.

For the initial mixture, 60 g of Benzoic acid in

powder form is dissolved in 25 l of boiling benzene.
The benzene - benzoic acid mixture is poured into
the equipment and continuously extracted using
distilled water.
After an extraction time of approx. 1 h the solvent
flow is switched to the extract vessel. A measure-
ment of the conductivity will show an increase in
the electrical conductivity of the water.
The solvent is fed from the extract vessel to the
distillation unit, to distil part of the water from the
mixture.
After a distillation time of 1 h, the conductivity of
the water is measured again.
The conductivity will change as follows.
Solvent before extraction: 0 µS

5 Experiments 32
 CE620 Liquid- Liquid Extraction

Solvent after extraction: 170 µS

Bottom product after distillation: 850 µS

The electrical conductivity of the water increases

with the concentration of benzoic acid in the water.

In the appendix there is a calibration curve for

benzoic acid in water.
The measurements should be performed using
the conductivity meter supplied. The conductivity
09/01

meter is not toleranced for measuring absolute

values. It is sufficiently precise for making relative
measurements indicating qualitative changes.
All rights reserved G.U.N.T. Gerätebau GmbH, Barsbüttel, Germany

5 Experiments 33
 CE620 Liquid- Liquid Extraction

6 Appendix

6.1 Technical Data

Overall Unit:

Length x Width x Height: 1350 x 700 x 2100 mm

Weight: 200 kg

Supply: 230 V / 50 Hz
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Alternatives optional,
see type plate

Extraction column:
All rights reserved G.U.N.T. Gerätebau GmbH, Barsbüttel, Germany

Diameter x height 50 x 1500 mm

Material: DURAN glass
Tower packing: Raschig rings

Distillation unit:
Distillation vessel volume: 5l
Column dimensions (diameter x height): 30 x 450 mm
Tower packing: Raschig rings
Heater rating: 945 W

Feed pump:
Max. pump rating: 1.1 l/min
Max. pressure: 10 bar
Rating: 180 W

Solvent pump:
Max. pump rating: 0.315 l/min
Max. pressure: 6 bar

6 Appendix 34
 All rights reserved G.U.N.T. Gerätebau GmbH, Barsbüttel, Germany 09/01

6.2
CE620

6 Appendix
LoadingConductivity

Conductivity
Calibration curve water- benzoic acid

Loading
Liquid- Liquid Extraction

35