Liquid/Liquid Separations (Extraction)

Liquid extraction = mass transfer of a solute from a liquid by contact with another liquid.
The two bulk liquid streams are relatively insoluble in each other (forming two liquid
phases) but the solute is soluble in both liquids.

Heavy Liquid Inlet Light Liquid Outlet

Feed = Diluant (L) liquid phase containing unwanted solute a

(or A)

Separating agent = (V) liquid phase in which primarily only a

Separation device is soluable
=
Products = (L) solute-free raffinate + (V) enriched extract
column (either
streams
continuous or
staged)
Principle of separation = preferential solubility

Heavy Liquid Outlet Light Liquid Inlet

Extraction is used when combined extraction & solvent recovery are more economical
than a more direct separation like distillation….for example
♦ when solute is present in very low initial concentration (organic in water)
♦ temperature sensitive materials
♦ close boiling mixtures with different chemical structures

Applications = separation of paraffin from aromatics, manufacture of p-xylene from

crude oil, improve purity of lubricating oils, purification of vegetable oil, separation of
saturated fats from unsaturated fats, recovery of penicillin

Extraction Equipment = goal is to bring two liquid phases into good contact to enhance
mass transfer…phases are then separated. In extraction, mixing is not so easy as
absorption or distillation….liquid phases are viscous and linear velocities in column are
low, therefore mechanical agitation is often used.
♦ Mixer-settler
♦ Spray column
♦ Packed column
 ♦ Plate or baffle column
♦ Agitated tower

Principles of Extraction = Continuous Extraction Processes use countercurrent contact

between light phase and heavy phase. Many of the same principles used in absorption &
distillation apply to extraction:
♦ Minimum ratio of light phase flowrate/heavy phase
♦ Number of ideal stages (or column height)
♦ Stage efficiency
♦ Column diameter and design of internal components

Differences between Extraction and Absorption or Distillation:

♦ Liquid/Liquid Equilibrium is more complicated than binary distillation or
absorption if all three components transfer & are present in each phase

Equilibrium Expressions for Liq/Liq System

Notation for Liq/Liq Systems Depicted on the Equilateral Triangular Diagram Below
Solute a in solution with Diluent b
Solvent s is used to extract solute a
Solvent Rich Stream = Extract = V
Diluent Rich Stream = Raffinate = L

Equilibrium for 2 liquid phases containing 3 components (2 bulk liquid components and
1 solute specie) F = 3-2+2 = 3 degrees of freedom

Equilibrium data are presented on Triangular Diagrams for 3 component Liq/Liq

system. Features of the Diagram
1) Each of the three corners represents a pure component a, b, and s
2) Point M in the interior of the triangle represents a mixture of a, b, and s. The
perpendicular distance from M to the base s-b represents the mass fraction of “a” (xa) in
the mixture , the distance from M to the base s-a = mass fraction of b and the distance
from M to the bas a-b = mass fraction of s.
3) Common phase diagram where s and b are partially miscible in each other is shown
below

4) the area inside the dome shaped region is the 2 phase region. Any overall
composition that falls inside this area will separate into two phases - point C=comp of the
extract (or solvent) rich layer & point D=comp of the raffinate (diluent) layer
5) Points representing phase equilibrium compositions are joined by tie lines. Point P is
the Plait point, where the composition of the extract layer = composition of the raffinate
layer
6) When tie lines slope up to the left (extract phase is richer in solute than raffinate
phase), solute can be extracted from the diluent using only moderate amounts of solvent.
When tie lines slope up to the right, extraction is still possible, but more solvent would be
needed.
7) When pure solvent is added to a binary mixture of diluent + solute (b+s) and allowed
to come to equilibrium, the composition of the resulting mixture lies on a straight line
between the "pure solvent" point s and the point representing the original binary mixture
a+b. Single stage extraction calculations can be performed this way.
Since Triangular diagrams have some disadvantages because of the special coordinates, a
more useful method of plotting the three equilibrium data is to use Rectangular
coordinates.
Two different methods of plotting equilibrium data are shown below.

Upper plot - Mass fraction of Solute ‘a’ (xa, ya) vs Mass fraction Solvent ‘s’ (xs, ys )
Lower plot - Diluent Layer composition of ‘a’ (xa) vs Solvent Layer composition of ‘a’
(yA).
Single Stage Extraction Calculation (calc outlet compositions and flowrates)

Extract
V Solvent
Isopropyl ether +
Isopropyl ether
Acetic acid

Raffinate
L Feed
Water +
Water +
Acetic acid
acetic acid

The single stage extraction shown above can be represented this way
V, ya, ys
M, xaM, xsM

L, xa, xs

Streams exiting the stage are assumed to be in equilibrium

Known Quantities = L, xa, xs, V, ya, ys

Unknown Quantities = exiting composition and flowrates of the raffinate and extract
streams

Total Material Balance to find M, xaM, and xsM:

Graphical Solution:
♦ Using Triangular phase equilibrium diagram
mentioned earlier

♦ Using the "mass fraction a vs mass fraction s" diagram

1) composition pairs (xa, xs) of streams that are added together lie on a straight
line i.e. for the single stage operation, the composition pairs (xa, xs) representing
stream L, and (ya, ys) representing stream V lie on a straight line
 2) Point M represents the overall composition of streams that are added (L+V =
M) and its composition (xaM, xsM) also lies on the line between L and V

3) the ratio of flowrates L/V = line segment length VM/line segment length LM
This is called the Inverse Lever Arm Rule

Continuous Multistage Countercurrent Extraction Design

Number of Stages
McCabe-Thiele method L0, x0 V1, y1
Perform an overall mat’l balance to determine terminal
compositions and flowrates…this is complicated 1
by the fact that all 3 components exist in 2 phases
requiring an iterative solution L1, x1 V2, y2

Operating line: 2

Plot L/V (the operating line) on a "conc of a in the L2, x2 Vn, yn

Extract vs conc of a in the raffinate” equilibrium plot
this is complicated by the fact that all 3 components n
exist in 2 phases requiring an iterative solution
Ln, xn Vn+1, yn+1
Step off stages between the operating line and equilib
Curve (This example is exactly like absorption)
LN-1, xN-1 VN, yN

LN, xN VN+1, yN+1

Number of Stages
Kresmer Equation Method (assumes constant L/V and straight equilibrium line)
If Solvent S and Diluent B are relatively immiscible in each other and if solute A
is relatively dilute this procedure can be greatly simplified

If the equilibrium is a straight line “ya= KDxa” you can define an extraction factor
E where E = KDV/L

(equivalent to stripping factor in Chap 20) and use the Kresmer Equations
(MSH 20.28) to calculate N

N=
[( )]
ln x a − x a* ) /( xb − xb*
ln E
subscript a and b in the Kresmer eqn refer to compositions of the solute at the top
and bottom of the column respectively. In extraction, x =mole fraction in the
raffinate and y =mol fraction in the solvent

Number of Stages
Rigorous Solution Method (graphical)
Overall Material Balance (to determine Terminal Compositions and Flowrates
and to determine the coordinates of point M)

L0, x0 V1, y1

L1, x1 V2, y2

2
Derivation of Operating Point (Delta Point)
L2, x2 Vn, yn

Ln, xn Vn+1, yn+1

LN-1, xN-1 VN, yN

Graphical Construction to determine Number of Stages LN, xN VN+1, yN+1

1) Using the Mass Frac A vs Mass Frac S diagram, locate points VN+1, LN, L0,
and V1 (use the coordinates of the M point to help locate V1)
2) Intersect the two lines LN VN+1 and L0 V1 to locate the Delta Point
(or use the formulas derived for the delta point to find it)
3) V1 and L1 lie on a tie line. Determine L1 using the tie line through V1
 4) Draw a straight line from L1 to delta point (this is the OPERATING LINE).
The intersection of this line with "extract portion" of the mutual solubility curve
gives V2.
5) V2 and L2 lie on a tie line. Determine L2.
6) Draw a straight line from L2 to delta point. The intersection of this line with
the mutual solubility curve gives V3.
7) Continue in this manner until LN is reached.
8) Each tie line used denotes a single stage. Count the number of stages.
9) Once the compositions of the streams leaving and entering each stage are
determined, the next step is to determine the flowrates. This can be done using
material balances on each stage or by using the Inverse Lever Arm Rule

Minimum Solvent Flowrate for Extraction

If solvent rate VN+1 is too low separation is not possible because operating lines
for streams passing each other coincide (lie directly on top of) equilibrium tie
lines for streams exiting the stage (infinite stages are required)

To find the Minimum Solvent flowrate

1) Locate point L0 and the equilibrium tie line through that point
2) Draw this tie line to intersect with the "extract" layer of the mutual solubility
curve
3) This point is V1min
4) Draw the lines LNV1min and L0VN+1 to find the location of Mmin (i.e. xAMmin)
5) Use a overall material balance and xAMmin to solve for VN+1

Solid/Liquid Separations (Leaching)

Leaching = removal of a solute from an insoluble solid by contact with a liquid solvent.
Overflow product Separating Agent
Solvent+Solute Liquid Solvent
Separation device=
Countercurrent cascade
Feed
Underflow product
Solid + Solute
Solid + Solvent+Solute

Feed = Solids (L) containing unwanted solute A

Separating agent = (V) liquid in which only A is soluable

Products = (L) solute-free solid (underflow)

(V) liquid containing solute (overflow)

Principle of separation = preferential solubility

Applications = used in food processing industries to produce sugar from sugar beets,
vegetable oil from peanuts. Also used in pharmaceuticals obtained from plants and in
metal recovery

Solid Preparation = prior to leaching solids are crushed to improve mass transfer. During
the course of leaching the solids may change considerably

Mechanisms for leaching =

Multiple steps take place in transferring a solute out of a solid

Leaching Equipment = goal is to bring solid and liquid phases into good contact to
enhance mass transfer…phases are then separated. In leaching, the solid may be
dispersed in the liquid or the liquid may be percolated through a fixed bed of solids.
Leaching can be operated as a batch or continuous process
♦ Series of stationary solid-bed tanks operated countercurrently
♦ Moving-bed leaching

Principles of leaching = Continuous countercurrent contact using stages is most common

method of leaching. Many of the same principles used in absorption & distillation apply
to leaching:
♦ Number of ideal stages (based on equilibrium and operating lines)
♦ Stage efficiency

Equilibrium Expressions for Solid/Liq System

Assumptions:

Notation for Solid/Liq Systems

Underflow = solid-liquid stream exiting a stage (L= kg/hr liq associated w/ solid)
Overflow = liquid stream exiting a stage (V=kg/hr A+S)
A= kg solute
B= kg solid (bone dry solid)
S= kg solvent
N=kg B/kg A+S
XA= kg A/kg A+S in overflow
YA=kg A/kg A+S in underflow
Graphical Representation of equilibrium data (N vs x,y)

Single Stage Leaching Calculation (calc outlet compositions and flowrates)

V1, X1 v2, x2
overflow Solvent

Lo, No, yo, L1, N1, y1,

B B
Feed solid underflow

L=kg/hr of liquid associated with the solid

Streams exiting the stage are assumed to be in equilibrium

Known Quantities = B, Lo, yo, x2, V2,

Unknown Quantities = exiting composition and flowrates of the raffinate and extract
streams

Total Material Balance to find M, xM, and NM M:

Graphical Solution:
Using N vs x,y phase equilibrium diagram
Lo, V2, M lie on straight line= use this to find location of M
L1, V1, M lie on straight line (equilibrium tie line)= use this to find exiting
compositions and relative flowrates
 Example- Single stage leaching:

Continuous Multistage Countercurrent Extraction Design

Number of Stages
Rigorous Solution Method (graphical)
Overall Material Balance (to determine Terminal Compositions and Flowrates
and to determine the coordinates of point M)

Operating Point (Delta Point)

Graphical Construction to determine Number of Stages similar to leaching

(see handout)