LIQUID-LIQUID EXTRACTION

(LLE)
 INTRODUCTION
 Liquid–liquid extraction (LLE) also known as solvent extraction, is a method to
separate compounds based on their relative solubility in two different immiscible
liquids, usually water and an organic solvent.
 It consists of transferring one or more solute contained in a feed solution to
another immiscible liquid (solvent).
It depends on the mass transfer of the component to be extracted from a first liquid
phase to a second one.
Separation is achieved when the substances constituting the original solution is
transferred from the original solution to the other liquid solution
 OUTPUT

 Introduction
 Purpose of Extraction
 Definition
 Theory
Fundamental principles of LLE
Methods of Extraction
Types of extractors
Choice of solvent
Advantages of solvent extraction
Application of Extraction
 Discussion
 End
 References
 PURPOSE OF EXTRACTION

 To separate closed-boiling point mixture

 Mixture that cannot withstand high temperature of distillation

Example: - recovery of penicillin from fermentation broth solvent:

butyl acetate - recovery of acetic acid from dilute aqueous solutions

solvent: ethyl-acetate
 DEFINITION
Three components are involved in the LLE process:
solute, diluent, and extractant.
Solute, which is dissolved in diluent, is extracted from the diluent and dissolved
into another solvent, the extractant.

 
 solute: species we aim to recover (A) from the feed
 feed or “feed solvent”: one of the liquids in the system (“carrier”)
 solvent: MSA (by convention: the “added” liquid)
 extract: solvent (not solute) mostly present in this layer.
 THEORY

Fundamental principles of LLE

The LLE process is based on the solubility of solute in different solvents.
For a given system, the solute will distribute in different solvents at a certain
partition ratio, and this ratio will not change as the system reaches equilibrium.
The properties of the LLE system, and some important definitions, are as follows:
 o Equilibrium partition ratios

In the ideal equilibrium state, the solute concentration is low enough that every
solute molecule is surrounded by solution and the two phases of the dissolved
solute are in the same molecular state; therefore, the weight fraction of solute in
extractant (y) divided by the weight fraction of solute in the diluent (x) at the given
stable condition is constant, termed partition ratio (K), as shown in Eq. (3.1):

( 3.1)
 o Distribution coefficient

In a real situation, the solute will be at different states in different phases, and
different states of solute will exchange depending on the solution. Therefore, the
partition ratio is not a constant it will change as the extractant changes Eq. (3.2):
• The distribution constant K, must be greater than 1 if the desired product is extract stream.
• The distribution constant K, must be lesser than 1 if the desired product is raffinate stream .

(3.2)
o Separation factor
The separation factor is a dimensionless factor that measures the relative enrichment of
solute in extractant after the LLE process. the separation factor is a parameter to describe
the selectivity of solvent, as in Eq. (3.3).

( 3.3)
 o Extraction factor

The extraction factor is defined as the total amount of solute in the extractant phase divided
by total amount solute in the raffinate phase.
For many commercial processes, the extraction factor is in the range of 1.3 to 5.
The extraction factor depends on the operation factors, such as temperature, solution
volume, and concentration of salt in solution.
 METHODS OF EXTRACTION

Three basic methods of liquid-liquid extraction are generally utilized in the analytical
laboratory.

A) Batch extraction
• Batch extraction, the simplest and most commonly used method, consists of
extracting the solute from one immiscible layer in to other by shaking.
• This is commonly used on the small scale in chemical laboratories.
• The most commonly employed apparatus for performing a batch extraction is a
separatory funnel.
• The batch extractions may also be used with advantage when the distribution ratio is
large.
 
B) Continuous extraction
• Continuous extraction, makes use of a continuous flow of immiscible solvent
through the solution or a continuous countercurrent flow of both phases.
• Continuous extractions are particularly applicable when the distribution ratio is
relatively small.
• Continuous extraction device operate on the same general principle, which consist
of distilling the extracting solvent from a boiler flask and condensing it and
passing it continuously through the solution being extracted.
  
C) Countercurrent extractions
• Extraction by continuous countercurrent distribution is the third general type and
is used primarily for fractionation purposes.
• The separation through continuous countercurrent method is achieved by virtue of
the density difference between the fluids in contact.
• The choice of method to be employed will depend primarily upon the value of the
distribution ratio of the solute of interest, as well as on the separation factors of
the interfering materials.
 
 TYPES OF EXTRACTORS

These extractor types can be categorized into three groups:

 The static extraction column
The static extraction column is an extractor without any stirring mechanism to
separate the extractant from diluents. As shown in Figure 3.6
 The rotary or agitated column,
Agitated columns were developed in order to control the efficiency of LLE. Three types
of major agitated columns are illustrated in Figure 3.7
  The centrifugal extractor
 The centrifugal extractor is an advanced design to separate extractant from diluents
using a rapid centrifuge. Figure 3.8 shows the basic structure of a centrifugal extractor .
 CHOICE OF SOLVENT

Factors to be considered:
 Selectivity
 Distribution coefficient
 Insolubility of solvent
 Recoverability of solute from solvent
 Density difference between liquid phases
 Interfacial tension
 Chemical reactivity
 Cost
 Viscosity, vapour pressure
 Flammability, toxicity
The requirements for extractants are as follows:

• the solute should be easily separated from extractant after the LLE.
• a high partition ratio is another property allowing effective separation of a
desirable compound from the diluent.
• the extractant should have high solubility for the target solute and low solubility for
the diluent.
• the extractant should have a different density from diluents for easy layering.
• low toxicity for the extractant and diluents is needed for industrial use.
 ADVANTAGES & DISADVANTAGES

Advantages
 accurate determination of water saturation
 non-destructive to core samples
 determination of water saturation by solvent extraction can be made part of the
core sample cleaning process for small incremental cost

Disadvantages
x slow (can take several days)
x oil volume not directly measured
x oil remains in solvent
 APPLICATION OF EXTRACTION

 Some solvent extraction is done physically by centrifuging.

The solution is spun at high speeds until most of the solvent has been extracted.

 To further extract any more volatiles , air or oven drying techniques are used.

 You can also extract solids from solvent by coagulating the solids in the solvent
and extracting the resulting lumpy matter.
 DISCUSSION
 When choosing the solvents for liquid-liquid extractions, what characteristics must they
have?
1) First solvent would preferably completely dissolve both compounds in the mixture
2) Second solvent selected must be immiscible with the first solvent
3) Second solvent should preferentially dissolve only one component of the original mixture
 What happens when we repeat the extracting step many times?
We add a fresh portion of the solvent to separatory funnel containing original solution of mixture, to
ensure that we get best possible separation
 Why are emulsions a bad thing?
Until the layers become distinct again, a separation is not possible.
 What is liquid liquid extraction based upon?
It is based on the differences in solubility of the components in two immiscible solvents
 END
The first commercially-successful liquid-liquid extraction operation was developed for the
petroleum industry in 1909 when Edeleanu's process was employed for the removal of
aromatic hydrocarbons from kerosene, using liquid sulfur dioxide as solvent.

This slide deals with the advances in the development of solvents for liquid–liquid extraction:

• The future will bring a further increase in concern over the environmental impact of chemical
operations.
• This requires the removal of hazardous substances.
• For many of the dilute waste solutions, solvent extraction has proved to be an effective process.
• In principle, solvent extraction is an environment-friendly process with no air or water
pollution.
• It could, therefore, replace many of the present polluting processes.
 REFERENCES

 Prof. Mukesh Doble- Liquid-Liquid Extraction- Indian Institute of Technology, Madras- Lecture – 8-page,3
 Prof. Mukesh Doble- Liquid-Liquid Extraction- Indian Institute of Technology, Madras- Lecture – 7-pages 7,6
 Frederick F. Cantwell and Manon Losier - Liquid-liquid extraction -Chapter 11 – page, 297
 Jianguo Zhang and Bo Hu - Department of Bioproducts and Biosystems Engineering, University of Minnesota,
USA- Liquid-Liquid Extraction (LLE)- pages ,62,63,65,66,68,69.
 J. Stary, “The Solvent Extraction of Metal Chelates”, Pergamon, Oxford, (1964).
 Organic Chem I 1 Alternative Title: “Shake it all out!”- Experiment #2- Liquid/Liquid Extraction – page3
 © Kevin Dunn, 2013 - Separation Processes: Liquid-liquid extraction -ChE 4M3 – page10
 http://www.ux.uis.no/~s-skj/ResTek1-v03/Notater/Tamu.Lecture.Notes/Saturations/Lecture_22.ppt
 https://www.quora.com/What-is-the-application-of-solvent-extraction-in-chemistry
 https://www.stscanadainc.com/liquid-liquid-extraction.html
 https://www.slideshare.net/karnavrana007/liquid-liquid-extraction-1