Chapter 13

Immiscible Extraction,
Washing, Leaching and
Supercritical Extraction

Chapter 13
Motivation:
13.1,
13.2,
13.3,
13.4,

Extraction
Extraction is a process where one or more
solutes are removed from a liquid by transferring
the solute(s) into a second liquid phase.
The second liquid phase, the solvent, is a mass
separating agent that must be recovered later.
The two liquid phases must be immiscible (that
is, insoluble in each other) or partially immiscible.

Require the addition of a mass-separating agent

Remove solute from a diluent (1st liquid

phase) by transferring it to a solvent
(2nd liquid phase)
Based on different solubility of solute in the 2
phases
4

The separation is based on different solubilities

of the solute in the two phases. Since
vaporization is not required, extraction can be
done at low temperature

suitable for unstable molecules such as DNA and proteins

Petrochemistry:
BTX separated from paraffins with sulfolane
5

Figure 13-1. Complete extraction process

Efficient contacting and separating of two liquid phases is considerably
more difficult than contacting and separating a vapor and a liquid

Solvent recovery using distillation or stripping is

more expensive than actual extraction
6

Figure 13-2. Extraction equipment

Table 13-1. Extractor types

Extractor

Examples

Unagitated
columns

Plate columns;
packed columns;
spray columns

General
Features
Low capital cost
Low operating and
maintenance cost
Simplicity in
construction
Handles corrosive
material

Mixer-settlers

Mixer-settler;
vertical mixersettler; Morris
contactor; static
mixers

Relatively low
efficiency
Higher-stage
efficiency
Handles wide
solvent ratios
High capacity
Good flexibility
Reliable scale-up
Handles liquids

Table 13-1. Extractor types

Pulsed columns

Perforated plate;
packed

Low HETP
No internal moving parts,
but mechanically complex
Many stages possible

Rotary-agitation
columns

Karr column often less

expensive
Reasonable capacity
Reasonable HETP

Rotating disk
contactor; OldshueRushton; Scheibel
Many stages possible
(several types); Kuhni;
Reasonable construction
asymmetric rotating
cost
disk
Low operating &
maintenance cost
Reciprocating-plate Karr column;
High throughput
columns
segmental passages; Low HETP
counter-moving plates Great versatility and
flexibility
Simplicity in construction
9

Handles liquids containing

Table 13-1. Extractor types

Centrifugal extractors Podbielniak;

and separators
Quadronic; AlfaLaval; Westfalia;
Robatel

Membrane extractors Celgard membrane

High capital &

operating costs
Short contacting time
for unstable material
Limited space
required
Handles easily
emulsified material
Handles systems with
little liquid density
difference
Up to 7 equilibrium
stages
High throughputno
flooding
Emulsion not formed
Chemical
compatibility may be
10
a problem

The following heuristics are useful for

making an initial decision on the type of
extraction equipment to use:
If one or two equilibrium stages are required, use
mixer-settlers.
If three equilibrium stages are required, use a mixersettler, a sieve tray column, a packed column (random
or structured), or a membrane contactor.
If four or five equilibrium stages are required, use a
sieve tray column, a packed column (random or
structured), or a membrane contactor.
If more than five equilibrium stages are required, use
one of the systems that apply mechanical energy to a
column (Figure 13-2).
11

The most common type of extraction cascade is the

countercurrent system

Figure 13-3. Mass balance envelope for countercurrent

cascade

In this cascade the two phases flow in opposite

directions.
Each stage is assumed to be an equilibrium
stage so that the two phases leaving the stage are
in equilibrium

12

The solute, A, is initially dissolved in diluent, D,

in the feed

Solute is extracted with solvent, S

The entering solvent stream is often presaturated
with diluent.
Streams with high concentrations of diluent are
called raffinate
While streams with high concentrations of solvent
are the extract
13

14

McCabe-Thiele Method for Dilute

Systems
The McCabe-Thiele analysis for dilute immiscible extraction
is very similar to the analysis for dilute absorption and
stripping discussed in Chapter 12.
In order to use a McCabe-Thiele type of analysis we must
be able to plot a single equilibrium curve, have the energy
balances automatically satisfied, and have one operating
line for each section.
For equilibrium conditions, the Gibbs phase rule is:
F = C P + 2.
There are three components (solute, solvent, and diluent)
and two phases. Thus, there are three degrees of freedom.
15

In order to plot equilibrium data as a single curve, we must

reduce this to one degree of freedom

Assumptions:
1. The system is isothermal
2. The system is isobaric
3. The heat
negligible

of

mixing

is

4. Diluent and solvent are

totally immiscible
5. R=FD=constant
and

16

Mass Balance using

envelope
Operating line
Since R/E is assumed to be constant, this equation plots as a straight line on a y vs. x
(McCabe-Thiele) graph
Rj
Raffinate flow rate leaving stage j, kg/h
Ej

Extract flow rate leaving stage j, kg/h

Equilibrium
curve data for dilute extraction are usually represented as a distribution ratio, K
Equilibrium
in weight fractions mole fracs, or concentrations (e.g., kg/m 3)

17

For very dilute systems Kd will be constant, while at higher concentrations

Kd often becomes a function of concentration

18

Kd(T)

see Table 13-3 for Acetic Acid/Benzene/Water

system

Kd low

Benzene is not a good solvent for

acetic acid because the Kd values are low but water
would be a goodKsolvent
if benzene were the diluent
d(T,pH)
The equilibrium constant is
temperature- and pHdependent

Vary pH (pH swing) to extract and recover penicillin

Solvent selection: nontoxic, noncorrosive, readily
available, chemically stable, inexpensive,
environmentally friendly.
Green solvents are now preferred
19

The McCabe-Thiele diagram for extraction can be obtained by

plotting the equilibrium data, which is a straight line if K d is
constant, and the operating line, which is also straight if
assumption 5 (constant total flow rates) is valid.

Operating line
slope=R/E
y-intercept= y1-(R/E) x0
goes through: (x0,y1) and
(xN,yN+1)
20

Example 13-1. Dilute countercurrent

immiscible extraction
A feed of 100.0 kg/min of a 1.2 wt % mixture of
acetic acid in water is to be extracted with 1butanol at 1 atm pressure and 26.7C. We desire an
outlet concentration of 0.1 wt % acetic acid in the
exiting water. We have available solvent stream 1
that is 44.0 kg/min of pure 1-butanol and solvent
stream 2 that is 30.0 kg/min of 1-butanol that
contains 0.4 wt % acetic acid. Devise a scheme to
do this separation, find the outlet flow rate and
concentration of the exiting 1-butanol phase, and
find the number of equilibrium contacts needed.
21

Figure 13-4. Dilute extractor with two feeds (Example 13-1);

(A) schematic, (B) McCabe-Thiele diagram

22

Kremser method for dilute systems

If one additional assumption can be made, the Kremser equation can
be used for dilute extraction of single or multicomponent systems

Assume Equilibrium is linear.

The grouping mE/R is

known as the extraction
factor

Other forms of the Kremser equation can also be written with

23

Single-stage and cross-flow extraction

nter-current is most common but occasionally can use cross-

Figure 13-8. Cross-flow cascade

Fresh extract streams are added to each stage

Extract product is removed
24

5 assumptions see for countercurrent case are also taken he

can use the McCabe-Thiele analysis

25

Mass balance around a single stage

Operating line is a straight line

Slope=-R/Ej (each stage will have a different operating lin

Intercept=(xj-1 *R/Ej + yj,in)

26

wo outlet streams are in equilibrium and on the operating lin

Figure 13-9. McCabe-Thiele diagram for cross-flow

27

Example 13-2. Single-stage and

cross-flow extraction of a protein
We wish to extract a dilute solution of the protein alcohol dehydrogenase
from a aqueous solution of 5 wt % poly (ethylene glycol) (PEG) with an
aqueous solution that is 10 wt % dextran. Aqueous two-phase extraction
system is a very gentle method of recovering proteins that is unlikely to
denature the protein since both phases are aqueous (Albertsson et al.,
1990; Harrison et al., 2003). The two phases can be considered to be
essentially immiscible. The dextran phase is denser and will be the crossflow solvent. The entering dextran phases contain no protein. The
entering PEG phase flow rate is 20 kg/h.
If 10 kg/h of dextran phase is added to a single-stage extractor, find
the total recovery fraction of alcohol dehydrogenase in the dextran
solvent phase.
If 10 kg/h of dextran phase is added to each stage of a cross-flow
cascade with two stages, find the total recovery fraction of alcohol
dehydrogenase in the dextran solvent phase.
The protein distribution coefficient is (Harrison et al., 2003)
Kd = (wt frac protein in PEG, x)/(wt frac protein in dextran, y) = 0.12
28