MASS TRANSFER Nandana Chakinala

CONTENTS
Liquid-liquid extraction
Application
Choice of solvent
Liquid-liquid equilibrium
Temperature effect on triangular diagram
WHY EXTRACTION

Distillation not feasible in following situations

1. The components having relatively same volatility
2. The components have low volatility
3. The components are sensitive to high T
4. The solute present in feed solution is in smaller amounts
DISTILLATION VS EXTRACTION
Simple
Heat energy as separating agent
produces another phase
Phases are chemically similar but with
different concentration
Direct separation
Not economic for dilute solutions
Solvent extraction is elaborate
MSA produces another phase which is
chemically different
Phases are chemically different
Indirect separation
15% capital costs for extractor and
85% for solvent recovery
INTRODUCTION
✓Separation components of liquid solution (feed) by contact with another
insoluble/partially soluble liquid (solvent)
✓ No pure components are obtained
✓ Solute gets distributed between two phases, which are of different densities
✓ Extract: Solute rich phase/solvent rich phase (Solvent enriched with solute)
✓ Raffinate: Solute lean phase (residual liquid from which solute is removed)
✓ Advantage over Azeotropic distillation but not economic if distillation is easier
✓ Indirect separation method unlike distillation and evaporation
✓ Mostly extraction followed by distillation/evaporation
✓ Eg: Acetic acid-water using ethyl acetate
ADVANTAGES
Close boiling compounds and azeotropes
Separation of heat sensitive materials where extraction is less expensive than low P or
vacuum distillation
Recovery of solute from very dilute solutions

APPLICATIONS
Separation of BTX from petroleum fractions
Extraction of penicillin
Extraction of Caprolactum

The key to effective extraction process is a suitable solvent

• When a mixture consists of less than 50% acetic
acid, distillation is expensive
• B.P acetic acid = 118 oC
• B.P ethyl acetate = 77 oC
• Two distillations are to recover solvent for reuse
• F = 30,260 lb/h of 22wt% acetic acid is
contacted with 71,100 lb/h of ethyl acetate
solvent
• Low density solvent rich phase at top 99.8%
acetic acid in feed
• High density carrier rich phase at bottom 0.05
wt% acetic acid in feed
CHOICE OF SOLVENT
A & B are pure substantially insoluble liquid solvents, C is the solute
Same used to denote quantity of solution
Selectivity = (mass fraction of C in E/A in E)/ (mass fraction C in R/A in R)
Selectivity to be greater than 1, separation not possible if selectivity = 1
High affinity for the solute, from which it should be easily separated by distillation or
any other means
Distribution coefficient for the solute between liquid phases should be not necessarily
greater than 1 but large values are desirable or a larger solvent to feed ratio would
be required
Difference in densities of two liquid phases is desirable
Recoverability
Non toxic and non flammable
 LIQUID EQUILIBRIUM (TERMINOLOGY)
Mixture to be separated consists of A + C
A: solvent (carrier liquid)
C: Solute
B: Additional solvent being added to
extractor
E: mass/time of extract solution
R: mass/time of raffinate solution
Solvent free basis:
E’: mass/time of B-free solution
Note: Carrier liquid might consists of several other
components and solvent might be mixed solvent. In this case,
design is complicated
x: mass fraction of solute C in raffinate
solution (A-rich solution)
y: mass fraction of solute C in extract phase
(B rich phase)
x’: x/(1-x): mass C/mass non C in raffinate
phase
y’: y/(1-y): mass C/mass non C in extract
phase
X: wt fraction of C in raffinate on B free
basis = C/(A+C)
Y: wt fraction of C in extract on B free
basis= C/(A+C)
N: wt fraction of B on B-free basis =
C/(A+C)
EQUILIBRIUM DATA-TRIANGULAR DIAGRAM
In distillation, the equilibrium data can be generated using thermodynamic models,
Experimental data is preferred compared to activity coefficient models such as NRTL
and UNIQUAC
Ternary systems can’t be represented on rectangular coordinates but binary mixtures
can be.
Rectangular coordinates can be used for plotting mole/mass fractions of solute and
solvent in solvent free basis (B-free)
Equilateral triangle
Point M represents mixture of A, B,C
M consists of 16% A + 24% B + 60% C
MN1 +MN2 +MN3 = CT

Perpendicular distance from any point K to base AB

represents %C in mixture at K
Perpendicular distance from any point K to base AC
represents %B in the mixture
MATERIAL BALANCE
R kg of mixture added to E kg of another mixture to
give M kg of new mixture
Balance on C:

Eliminating M
CLASSIFICATION

1. A and B are immiscible

2. One pair partially soluble: A and B are partially miscible, where C is miscible in A and B in all
proportions/completely – TYPE I
 Benzene-water-Acetic acid

3. Two pair partially soluble: C miscible in A in all proportions, A-B & B-C show limited solubility
 Eg: Chlorobenzene (A)-water(B)-Ethyl ketone(C)

Equilibrium data can be plotted on

 Equilateral triangular diagram
 Right angle triangular diagram by representing two concentrations
 Rectangular co-od representing solute and solvent in two phases on solvent-free basis
TYPE I MIXTURES
P is the plait point
RP : Raffinate phase
PS: Extract phase
RPS is the equilibrium curve
G1H1 is the tie line representing two liquid phases at
equilibrium
K is a mixture of extract and Raffinate
TYPE I MIXTURES
TYPE II MIXTURES (C AND A LIMITED MISCIBILITY IN B)
No plait point
Extract and Raffinate arm does not meet
TYPE II MIXTURES

1. Points K , J represents mutual solubility of A

and B
2. Points H, L rep mutual solubility of B & C
3. Curve
4. KRH (A-rich) and JEL (B-rich) are ternary
solubility curves
5. Mixtures outside these curves represents
homogenous solution
TEMPERATURE EFFECT-TYPE I SYSTEMS
The mutual solubility of A and B increases with
temperature
Beyond a temperature, called as critical solution
temperature A and B are completely soluble
Area of heterogeneity decreases and the slope of tie
lines decreases as T increases
Extraction (depends on formation of insoluble liquid
phases) to be carried at T below critical solution
temperature
TEMPERATURE EFFECT-TYPE II SYSTEMS
Increased T increases mutual solubility and at the same
time influences slope of tie lines
Above critical solution T of binary B-C pair, converts to
Type-I system
PRESSURE EFFECT

Influence of P on equilibrium is small expect at very high P

Extraction to be carried out at a P greater than the vapour pressure of solutions
If V.P < Total pressure then vaporization can be avoided: Desirable
RIGHT ANGLED TRIANGULAR DIAGRAM- B FREE
BASIS

NXY diagram for two partially miscible pairs

RIGHT ANGLED TRIANGULAR DIAGRAM