Liquid-Liquid Extraction

Extraction schemes and Design of countercurrent

extractions

CHEN 312
 Extraction schemes
• Three frequently encountered extraction cascades are the co-current, crosscurrent
and countercurrent arrangements
Dilute Extraction Systems

Single equilibrium stage

• Consider the case that the solvent and the carrier are completely immiscible, the solvent
contains no solute and solute concentrations in the extract and raffinate remain low (< 1
%).
• Under these conditions:
The resulting extract flow will approximately equal the solvent flow, E ≈ S,
and the raffinate flow approximately equal the feed flow, R ≈ F.

• Thus the material balance over the solute in a single equilibrium stage becomes:
Equilibrium stages

• When equilibrium is reached in extraction, the stage is defined as an

ideal or theoretical stage and the equilibrium conditions can be
expressed in terms of the extraction factor E for the solute:

The larger the value of the extraction factor E, the greater the extent to which the solute it
extracted. Large values of E result from large values of the distribution coefficient, K, or large
solvent to carrier ratios.
where K is the distribution coefficient of the solute xE = [Link]
between the extract and the raffinate.

Note that, for dilute systems, K can be assumed constant throughout the
operation of the extraction system.
 Design of countercurrent
extractions
 For the dilute extraction system (i.e. the extraction system in which the
concentration of the solute is low), we can assume that:
 R ≈ FD and E ≈ S all in kg/s = constant
 Note that:
 R = raffinate flow rate
 E = extract flow rate
 FD (F’) = diluent flow rate
 FS (S’) = solvent flow rate
 Additionally, if the solvent and diluent are immiscible in each other, F D and FS

can be assumed to be constant throughout the system. 7

Design of countercurrent
extractions
When the carrier and solvent are immiscible, weight ratio units are related to
weight fractions as:

where X is kg solute/kg carrier and Y is kg solute/kg solvent.

Remember: Since adding large amounts of solute often makes the phases partially miscible,
the assumption of complete immiscibility is often valid only for dilute systems.
For the usual design problem, F′ /S′ will be known as well are
X0, XN and YN+1. Since XN and YN+1 are the concentrations of
passing streams, they represent the coordinates of a point on
the operating line.
 McCabe-Thiele analysis
Counter-current extraction with
immiscible liquids

• Equation of the operating line:

e
in
.l
Eq
( )
𝐹𝐷 𝐹𝐷 •X0
𝑌= 𝑋 + 𝑌 1− 𝑋
𝐹𝑆 𝐹𝑆 0

ax
)m S
/F
1 •(X0,Y1)

D
(F
•
e
( )
𝐹𝐷
𝐹𝑆 𝑚𝑎𝑥
𝑔𝑖𝑣𝑒𝑠 𝐹 𝑆 ,𝑚𝑖𝑛 𝑓𝑜𝑟 𝑁 =∞ 2
•
it n
•ra e =
li n
g

pe p
3 o sl o
• For dilute solutions, • • /D F S
F N=
3
𝑦=
𝑅
𝐸 (
𝑥 + 𝑦1 −
𝑅
𝑥
𝐸 0 ) •(XN,YN+1)
 Analytical Kremser method

In the case that the solvents are substantially immiscible and a constant distribution
coefficient the required number of theoretical stages, N ts, for countercurrent contact can
be calculated directly.
Example:

A feed of 100 kg/min of 1.2 wt% mixture of acetic acid in water is to be

extracted with 1-butanol at 1 atm and 26.7 oC. The desired outlet concentration
in the exiting stream is 0.1 wt% of acetic acid. The solvent of pure 1-butanol is
fed contercurrently to the feed with the flow rate of 75 kg/min.
 Determine the composition of the exiting 1-butanol phase.
 Also find the number of equilibrium contacts (stages) needed. KD

(Distribution coefficient) for acetic-water-1-butanol at 26.7 oC is 1.613.

13
In this case:
 The inlet concentration of the feed : xo =

0.012
 The outlet concentration of the raffinate: xn =

0.001
 The solvent is pure butanol, yn+1 = 0
 The flow chart for this operation is as follows:

14
  The concentration of the exiting extract phase stream can be computed
using operating line equation:

0=
100
75 [ ( )
( 0.001 ) + 𝑦 1 −
100
75
( 0.012 )
]
𝑦 1=0.015

Thus, the co-ordinates for the operating line:

( 𝑥 𝑁 , 𝑦 𝑁+ 1) =( 0.001, 0 )

( 𝑥 0 , 𝑦 1 ) =( 0.012 , 0.015 )

 Drawing operating and equilibrium lines and stepping off stages yields 6
equilibrium stages.
15
16
 Cross-flow Cascade

 From mass balance around stage j:

𝑦 𝑗 =−
𝑅
𝐸𝑗 (
𝑥𝑖 + 𝑦 𝑗 ,𝑖𝑛 +
𝑅
𝐸𝑗
𝑥 𝑗− 1
)
 Increase overall efficiency by introducing fresh extracting

solvent at each stage.

 Each stage has its own mass balance and operating line

 Uses much more solvent than counter-current cascade

(requires much more solvent recovery).

 Note that the slopes of equilibrium lines may not be equal to

one another, as the value of the flow rate of the extract

phase Ej at each stage may vary.

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Industrial liquid-liquid extractors

• [Link]
lications/
• [Link]
240085
• [Link]
Cascade Effi ciencies
Cocurrent Crosscurrent Countercurrent Countercurrent
FC,XA(F) B FC,XA(F) FC,XA(F) Extract
YA(1)

Extraction
Crosscurrent
Extract 1
1 B/2 1 1
YA(1) Cocurrent
XA(1) YA(1) XA(1) XA(1) YA(2)

2 B/2 2 2
Extract 2
XA(2)= XA(R) YA(2) XA(2)= XA(R) Raffinate YA(2) XA(2)= XA(R) Number of Stages
Raffinate Extract
B
Raffinate
X A(N ) 1
X A ( 2) 1 X (N )  X A(N ) 1
  A
X A (F ) 1  E X A (F )
X A ( F ) 1  E / N N N
X A (F )  E n
Increased separation but cannot
No additional separation. n 0
obtain arbitrary purity because
Added stages only useful
the solvent is divided into N If E > 1 then arbitrary
for increasing residence
stages. high purity can be
time.
obtained. If E<1
then 1-E times as much
A will remain in the
𝐾𝐷 𝐵 Where Fc is the flowrate of raffinate.
𝐸=
𝐹𝐶 19
the carrier liquid
Example:

Benzene is to be used to remove 95.0% of the dioxane in 0.278 kg s-1 of a

30.0 wt % dioxane in water solution. The benzene is initially dioxane free and
the equilibrium distribution coefficient KD is 1.20. Determine the solvent

requirements for the following configurations:

1. Single batch extraction;

2. Three crosscurrent stages using equal amounts of benzene;

3. Two counter-current stages;

20
Solution
 Feed F is 0.278 kg s-1 which has 30 wt % dioxane

 Hence FA = 0.278 x 0.30 = 0.0834 kg s-1

FC = 0.278 x 0.70 = 0.1946 kg s-1

 It is required to remove 95% of the dioxane.

 Hence 5% or 0.05 fraction of original remains in raffinate.

Therefore:

Extraction Factor is E where:

𝐾𝐷𝑆 1.2 𝑆
𝐸= = =6.17 𝑆 21
𝐹❑ 0.1946
1- For a single batch extractor

Therefore:

From equation therefore the required solvent flow

2- For three crosscurrent stages using equal amounts of benzene B

Hence E = 5.14
Using equation so solvent S is

2
3- For two countercurrent stages

Therefore: OR
Quadratic solution is

In this case :

Hence
Using equation then s-1

23
Question:

A water solution containing 0.005 mole fraction of benzoic acid is to be

extracted by pure toluene as the solvent. If the feed rate is 100 moles/h and
the solvent rate is 100 moles/h, find the number of equilibrium stages
required to reduce the water concentration to 0.0001 mole fraction benzoic
acid. Operation is isothermal and countercurrent.
The equilibrium represented by: mole fraction benzoic acid in water = 0.446 *
mole fraction benzoic acid in toluene.
Compare the McCabe-Thiele method with the analytical Kremser method.
Question:
Phenol is a toxic chemical that is used in the chemical industry for the production of
resins. It has a solubility in water of approximately 8 g/ 100g water, and for
environmental reasons it is important to treat process waters. Consider a 1000 kg
aqueous process water stream with 8 wt% phenol that is to be treated. Because of
its immiscibility with water, heptane is considered as solvent. The heptane is phenol
free. The distribution coefficient of phenol at low concentrations is constant and has
a value of KD = 0.2 (wtfr. phenol in heptane/wtfr. phenol in water).

Calculate the solvent requirements for removing 99% of the phenol in:
a)A single batch extraction
b)Two crosscurrent stages using equal amounts of heptane
c)Two countercurrent stages
d)An infinite number of crosscurrent stages
e)An infinite number of countercurrent stages