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• Introduction
• Important aspects in design and
operation of the extraction processes.
• Selectivity and Distribution coefficient
• Extraction techniques
• Extraction apparatus and equipment

Liquid-Liquid extraction is a mass

transfer operation in which a liquid
solution (the feed) is contacted with an
immiscible or nearly immiscible liquid
Diluent A and a solute B which are miscible.
The objective is to recover the solute
Two streams result from this contact: the extract,
which is the solvent rich solution containing the
desired extracted solute, and the raffinate, the
residual feed solution containing little solute.


A + eB
Partition between two phases
 Liquid/solid,
 gas/liquid,
 liquid/liquid

Partition based on relative solubility in the

two solvents
Two techniques:
 Macroscale, using a separatory funnel
 Microscale, using pipets and centrifuge tubes
Extraction Process
(in macroscale)

• Mixture dissolved in
solvent 1 & placed in
separatory funnel
• Immiscible solvent 2
added, stoppered &
• Mixture components
distribute according to
• Bottom layer drained
through stopcock to
separate phases
Microscale Extraction
• Mixture dissolved in
solvent 1 in a
centrifuge tube
• Immiscible solvent 2
added & agitated
• Bottom layer
removed with
Pasteur pipet &
transferred to clean
The following need to be carefully evaluated
when optimizing the design and operation of
the extraction processes.

•Solvent selection
•Operating Conditions (pH,T,P & residence time)
•Mode of Operation
•Extractor Type
•Design Criteria
Selection of solvent influenced by
• -its physico-chemical properties (allowing an easy
recovery of the solute or of the solvent),
• -a negligible solubility of the solvent in the diluent
(post-extraction processes have to be as cheap as
• -physical characteristics offering acceptable
dispersion and separation times of the post-contact
phases (viscosity, interfacial tension, density
difference compared to the feed),
• -favorable properties (Mass transfer kinetics –
equilibrium after contact less than a few minutes - ;
Economy – cheap and available solvent - ; Safety of
use – low toxicity, low flammability, low volatility,
low corrosion in comparison with usual
construction materials -),
But particularly a property called selectivity
Selectivity can be defined as the ability of the solvent to pick up the
desired component in the feed as compared to other components. The
desired properties of solvents are a high distribution coefficient, good
selectivity towards solute and little or no miscibility with feed
solution. Also, the solvent should be easily recoverable for recycle.

/ (mass fraction A in E) β>1

/ (mass fraction A in R)

This ratio is called the As for the second ratio, it is
distribution coefficient of always greater than 1 (there
the solute between the is more diluent in the raffinate
extract and the raffinate than in the extract
phases, m

The higher the m, the higher β and thus the more selective the solvent.

Consequently, a sufficient condition for a solvent to be selective is: m

greater than 1
Distribution ratio
In solvent extraction, a distribution ratio is often quoted
as a measure of how well-extracted a species is.
Partition or Distribution Coefficient
[𝐀]𝟏 𝐬𝐨𝐥𝐮𝐛𝐢𝐥𝐢𝐭𝐲 𝐨𝐟 𝐀 𝐢𝐧 𝐚 𝐬𝐨𝐥𝐯𝐞𝐧𝐭 𝟏
KD or D = = =
[𝐀]𝟐 𝐬𝐨𝐥𝐮𝐛𝐢𝐥𝐢𝐭𝐲 𝐨𝐟 𝐀 𝐢𝐧 𝐬𝐨𝐥𝐯𝐞𝐧𝐭 𝟐

𝐦𝐚𝐬𝐬 𝐀/𝐯𝐨𝐥𝐮𝐦𝐞 𝟏 (𝐦𝐚𝐬𝐬 𝐀)𝟏 𝐯𝐨𝐥𝐮𝐦𝐞 𝟏

= ●
(𝐦𝐚𝐬𝐬 𝐀/𝐯𝐨𝐥𝐮𝐦𝐞)𝟐 𝐦𝐚𝐬𝐬 𝐀 𝟐 𝐯𝐨𝐥𝐮𝐦𝐞 𝟐

For typical extractions:

solvent 1 = organic, solvent 2 = water

Example: solubilities of adipic acid @ 15°C

water (1.5 / 100 ml) ; ether (0.6g / 100 ml)
𝟎.𝟔𝒈 𝟏𝟎𝟎 𝒎𝒍
KD = ● = 0.40
𝟏.𝟓𝒈 𝟏𝟎𝟎 𝒎𝒍
Solvents for Acetic Acid Extraction
Solvent Distribution Miscibility with
Coefficient @ water
wt% @ 20C
n-Butanol 1.6 >10
Ethyl Acetate 0.9 10
MIBK 0.7 2.0
Toluene 0.06 0.05
n-Hexane 0.01 0.015

No solvent offers all possible favorable conditions. Thus, a

compromise has to be found between all the constraints.
Four extraction techniques

Single Counter-
stage current
with reflux
Cross- Counter-
current current

To design an extraction apparatus, it is necessary to:

- determine the number of ideal stages
- determine the phases flowrates, as well as the
solute distribution between the phases
- choose the most adapted apparatus
- study the hydrodynamics of the apparatus
- determine the size and the configuration of the
Centrifugal Extractor
Static / Agitated Columns

2. Paul Ashall 2007. Liquid-liquid extraction
3. Nadine LE BOLAY, Gilbert CASAMATTA.
Liquid extraction