Marco Mazzotti, Ian de Albuquerque

Liquid-Liquid Extraction: Part 1

Outline

Overview of Liquid-Liquid Extraction

Liquid-Liquid Equilibrium
Stability Criterion
Activity Coefficient Models
NRTL
UNIQUAC
Binary Phase Diagrams

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Overview of Liquid-Liquid Extraction

Extraction uses principles of Liquid-Liquid Equilibrium

Allow phases to settle

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Overview of Liquid-Liquid Extraction

Used when a solute (A) should be extracted from a Feed (F)

stream into a Solvent (S) stream, thereby cleaning F.
Solvent and diluent (D) are immiscible or partially miscible
e.g: aromatics separated from paraffins using sulfolane; metal
removal from waste water
Advantageous if components have close boiling points,
(b.p.s) very high or low b.ps
Solvent recovery may be costly (e.g. distillation )

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A step back: Connection with VLE

VLE

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A step back: Connection with VLE

VLE: non-ideality may lead to

azeotrope formation
Graph shows negative deviation
from Raoults Law

Molecules are attracted to

molecules of the other species

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A step back: Connection with VLE
VLE: non-ideality may lead to
azeotrope formation
Graph shows positive deviation
from Raoults Law

Molecules are repelled to molecules

of the other species
From an attraction/repulsion
standpoint, which case could
lead to liquid-liquid phase
splitting? D-MAVT/IPE/SPL | 27.04.2017 | 7
A step back: Connection with VLE

Extreme cases of non-ideality

result in LLE

upper consolute temperature

Mole fraction of component 1 in

Liquid phase
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A step back: Connection with VLE

Normally operating
temperatures are chosen
such that VLE is avoided.
Equilibrium calculation is
analogous to VLE:

Where both phases are liquid

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Outline

Overview of Liquid-Liquid Extraction

Liquid-Liquid Equilibrium
Stability Criterion
Activity Coefficient Models
NRTL
UNIQUAC
Binary Phase Diagrams

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Liquid-Liquid Equilibrium (LLE)

Equilibrium conditions can be formulated in terms of

chemical potentials as well
Used to introduce molar Gibbs free energy of mixing

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Liquid-Liquid Equilibrium (LLE)

Given that a mixture is in isothermal and isobaric

conditions all types of equilibrium can be expressed as

Where: is number of phases

is number of components
is mole fraction in phase
are temperature and pressure

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Liquid-Liquid Equilibrium (LLE)

For two liquids in equilibrium:

Written in terms of activities

Defining activities require defining a standard state

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Liquid-Liquid Equilibrium (LLE)

For liquid mixtures what kind of standard state makes

sense?
Ideal solution. Activity coefficients can be used:

Recall that for an ideal solution: Enthalpy of mixing, and

volume change upon mixing are zero
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Liquid-Liquid Equilibrium (LLE)

For two liquids in equilibrium:

Using the definition for activity

unknowns, equations. Underdetermined system

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 Liquid-Liquid Equilibrium (LLE) : Numerics

Incorporating material and stoichiometric balance

Note: Activity coefficient

weakly dependent on
pressure; functional
dependence omitted

unknowns, equations

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Gibbs free energy definitions
Liquid phase molar Gibbs free energy

In terms of activity coefficients

Recall that:
where G is Gibbs
free energy, and n
are number of mols

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Gibbs free energy definitions

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Gibbs free energy definitions

Mixtures at LLE have common tangent, e.g. :

Consider two mixtures with compositions and

Planes tangent to mixtures at these compositions are

given by (derivation uses Gibbs-Duhem relationship):

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Gibbs free energy definitions

If mixtures of compositions
given above are in equilibrium:

Tangent plane equations become:

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Outline

Overview of Liquid-Liquid Extraction

Liquid-Liquid Equilibrium
Stability Criterion
Activity Coefficient Models
NRTL
UNIQUAC
NRTL Parametric Study
Binary Phase Diagrams

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Stability Criterion

Why a stability criterion? Some advantages:

Clarifies whether a point in the phase diagram is stable, i.e. no liquid-
liquid phase separation, or not

LLE calculations are used for unstable compositions; thereby saving

lots of computational time
A priori, for ternary, quaternary and higher mixtures, it is not possible
to know where phase separation will occur

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Stability Criterion
Tangent plane distance function, at composition

stable if

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Stability Criterion
Tangent plane distance function, at composition

stable if

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 Stability Criterion
Tangent plane distance function, at composition

stable if

D is the space
between g
and L

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Outline

Overview of Liquid-Liquid Extraction

Liquid-Liquid Equilibrium
Stability Criterion
Activity Coefficient Models
NRTL
UNIQUAC
Binary Phase Diagrams

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Activity coefficient models

NRTL: developed by Renon and Prausnitz (1968)

Local-composition model
Composition related to interaction energy between different
molecules
Successful in describing many systems exhibiting LLE
Interaction parameters determined from various
equilibrium data (VLE, LLE, SLE)

UNIQUAC: group contribution method, that groups

molecules based on their functional groups. Powerful at
describing LLE
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Activity coefficient models

NRTL binary

Non-randomness and interaction energy

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Activity coefficient models

NRTL multicomponent

Ternary mixture:

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Parametric study

Hessian matrix of molar Gibbs free energy of mixing

contains information regarding stability

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Parametric study

Qualitative Example:

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Parametric study
Binary mixture

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Outline

Overview of Liquid-Liquid Extraction

Liquid-Liquid Equilibrium
Stability Criterion
Activity Coefficient Models
NRTL
UNIQUAC
Binary Phase Diagrams

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Binary Phase Diagrams

LLE in binary mixtures can be immediately read from molar

Gibbs free energy of mixing curve
Two liquids in equilibrium share a common tangent
NRTL: parameters dictate LLE symmetry and degree of
ideality

Symmetry Non-ideality

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Another Perspective: Solid-Liquid Equilibrium (SLE)

Pertinent case for

crystallization
LLE and SLE
What happens in
dashed region?
LLE and SLE interact.
LLE may precede SLE
avoiding/delaying solid
formation

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Another Perspective: Solid-Liquid Equilibrium

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Liquid-Liquid Extraction: Part 1

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Activity coefficient models

UNIQUAC: developed by Abrams and Prausnitz (1975)

Group contribution method
Idea is that contributions from each functional group can be
classified and quantified
Each molecule is built up from a combination of functional groups

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Activity coefficient models

UNIQUAC: developed by Abrams and Prausnitz (1975)

and are related to Van der Walls volume and area

respectively relative to a standard segment
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