Liquid Liquid Extraction

Ternary Diagram

Dr.
► solute: species we aim to recover (B) from the feed
► feed (F): one of the liquids in the system (“carrier”)
► Solvent (S): MSA (by convention: the “added” liquid)
► extract: solvent with extracted solute.
► raffinate: residual solute in this layer
x B = ratio of mass or mole of solute(B) to the mass/mole of
the other components in the feed (F), raffinate (R), or extract
(E).
We aim for the solute (B) to be mostly in the extract
stream.

2
Distribution of solute at equilibrium is

where K’DB is the distribution or partition coefficient in terms

of mass or mole ratios (instead of mass or mole fractions).

Combining above eq’s.

Another useful parameter is extraction factor (E) is

3
Substitute distribution coefficient in the above expression to get
the fraction of B not extracted,;

Alternatively the fraction of B extracted is

Mass (mole) ratio ‘X’ are related to mass (mole) fraction ‘x’
as;

Value of distribution coefficient in terms of fraction as;

Where (1) and (2) are solvent rich and solvent poor liquid
phases in equilibrium.
4
 Phase splitting of ternary mixture

A and C mutually insoluble A and C partially soluble

5
 Where/why LLE is used
Where?
► Bioseparations
► Nuclear (uranium recovery)
► Mining: nickel/cobalt; copper/iron
► Perfumes, fragrances and essential oils
► Fine and specialty chemicals

►Oil sands: extract bitumen away from water

Why?
► Temperature sensitive products
► High purity requirements
► High-boiling point species in low quantity
► Need to separate by species type (rather than
relative volatility)
► Close-boiling points, but high solubility difference
► Azeotrope-forming mixtures
6
Extractor types: 3 major steps required

1. Mixing/contacting:
) turbulent contact between liquid phases
) small droplet dispersion in a continuous
phase
) mass-transfer between phases
) limited by solute loading in solvent
2. Phase separation:
) reverse of above mixing step
) drops come together and coalesce
) relies on density difference
3. Collection of phases leaving the
unit
) split the raffinate from the extract 7
What are we aiming for?
Main aims
► High recovery of solute overall (low xR and high
xE )
How to achieve this?
► Cocurrent mixer-settlers
► Cross-current mixer settlers
► Counter-current mixer-settlers in series
► High interfacial area during mixing
► Reduce mass-transfer resistance
► Promote mass transfer: aim is to move solute in feed to
the solvent in extract stream
) molecular diffusion ← microscopic
) eddy diffusion ← orders of magnitude
movement
greater
8
Co-, cross-, counter-current
operations

9
 Selecting a solvent
“The choice of solvent for a LLE process can often have a
more significant impact on the process economics than any
other design decision that has to be made”.

Which properties of a solvent influence our aims with LLE?

► High distribution coefficient (selectivity) for solute
► Low distribution coefficient for carrier
► Reasonable volatility difference with solute and carrier
► Reasonable surface tension: easy to disperse and coalesce
► High density difference: separates rapidly by gravity
► Stability to maximize its reuse
► Inert to materials of construction
► Low viscosity: maximizes mass transfer
► Safe: non-toxic, non-flammable
► Cheap, and easily available
► Compatible with carrier and solute: avoid contamination
10
►
What are Ternary Phase Diagrams?
*Diagrams that represent the equilibrium
between the various phases that are
formed between three components, as a
function of temperature.
*Normally pressure is not a viable variable
in ternary phase diagram construction,
and is therefore held constant at 1 atm.
*A triangular phase diagram showing the
representation of the mass fractions
*One of the common ternary phase
diagrams is when liquid pairs A-B and B-C
are completely miscible in all proportions,
and the liquid pair A-C is only partially
miscible.
*This limited solubility of the A-C pair
causes two liquid layers to form.
*The concentration of each of the three
components can be expressed as either
“wt. %” or “molar %”
*The sum of the concentration of the three
components must add up to 100%
*The Gibbs Triangle is always used to
determine the overall composition
*The Gibbs Triangle: An equilateral triangle
on which the pure components are
represented by each corner
There are three ways of determining the
overall composition:

*Method 1
*Method 2
*Method 3
*Method 1
*Let the overall composition be represented by
the point X
*Draw lines passing through X and parallel to each
of the sides
*The line A’C’ intersects the side AB tells us the
concentration of component B in X
*The concentrations of A and C, in X, can be
determined in an identical manner
*Figures OC1 and OC2 shows the process
*Method 2
* Draw lines through X, parallel to the sides of the Gibbs
Triangle
A’C’ intersects AB at A’
B’C’’ intersects AB at B’

Concentration of B = AA’
Concentration of C = A’B’
Concentration of A = B’B
* This method can be somewhat confusing, thus, is not
recommended.
*Method 3
* Application of the Inverse Lever Rule
* Draw straight lines from each corner through X

NOTE:
Always determine the concentration of the components
independently, then check by adding them up to obtain 100%
26
CONCLUSION

The plotted ternary phase diagram yielded to two phase regions:

the one-phase region which was the upper region and the two-
phase region which is the lower region. Both regions have three
components and the degrees of freedom value for the upper
region is 4 while the lower region was 3. These number indicates
the intensive variables that is needed in each phases.

On the other hand, the tie line was drawn in the two-phase region
wherein its two points intersected the arc. Connecting these two
points together with the initial composition, the tie line was
divided into two portions. The left side would be the
concentration of components on the upper phase while the right
side represents the composition of the bottom phase.