Hunter Nash Liquid-Liquid Extraction

Last lecture: We used McCabe-Thiele to analyze multistage binary distillation in the

cases of:
• Side streams
• Multiple feed streams
• A partial condenser
• Open steam
We discussed the algebraic procedure for the distillation analysis
We discussed using a spreadsheet to efficiently analyze the distillation process

Today’s Lecture Covers:

Multistage Liquid-Liquid extraction

Specifications for liquid-liquid extraction cascades
Product points
Operating lines and operating points
The Hunter-Nash Procedure
Hunter-Nash graphical construction
Stepping off stages
Minimum solvent

Lecture 14: Hunter Nash 1

 Liquid-Liquid Extraction
Liquid-liquid Extraction of ternary systems involves contacting two equilibrium liquids where
the solvent liquid is immiscible or nearly immiscible with one of the components of the feed
liquid and miscible with one or more of the other components.

Liquid-liquid extraction is also referred to as:

•Extraction
•Solvent extraction
•Liquid extraction

In Section 4.5 we used the Ternary Phase Diagram to analyze Liquid-liquid Extraction for a single equilibrium stage.

Ternary Phase Diagram

Solvent: TCE
Solute: Acetone
Carrier: Water

Lecture 14: Hunter Nash 2

 Ternary Single-Stage Flash Separation
Solute

Plait Point
P

Extract
F
Feed
E
Mixing point
R Raffinate

Tie-lines

Solvent C Carrier
Lecture 14: Hunter Nash 3
 Liquid-Liquid Extraction Cascades

What if we have a countercurrent cascade of Liquid-Liquid contacting stages?

Solvent C
E1 E2 E3 En En+1EN-1 EN
Extract S
1 2 n N–1 N Raffinate
F R1 R2 Rn-1 Rn RN-2 RN-1 RN
Carrier A (FA)
Solute B (FB)

Can we use a similar analysis to the one we used for countercurrent leaching where
we had two condensed phases and complete immiscibility of the carrier in the solvent?

Yes, but different since in the liquid-liquid case we assume that we can disengage the phases
and we don’t have complete solubility.

Can we use a similar analysis to the one we used for countercurrent absorption or stripping?

Yes, but different since equilibrium here is given by a liquid-liquid ternary diagram rather
than a vapor-liquid equilibrium.

Lecture 14: Hunter Nash 4

 Liquid-Liquid Extraction: Specifications
Solvent C
E1 E2 E3 En En+1EN-1 EN
Extract S
1 2 n N–1 N Raffinate
F R1 R2 Rn-1 Rn RN-2 RN-1 RN
Carrier A (FA)
Solute B (FB)

Specifications: F, (xi)F, (yi)S, T and one of:

1) S and (xi)RN
2) S and (yi)E1
3) (xi)RN and (yi)E1
4) N and (xi)RN
5) N and (yi)E1
6) S and N

Lecture 14: Hunter Nash 5

 Hunter-Nash Solution for Liquid-Liquid Extraction
Solvent C
E1 E2 E3 En En+1EN-1 EN
Extract S
1 2 n N–1 N Raffinate
F R1 R2 Rn-1 Rn RN-2 RN-1 RN
Carrier A (FA)
Solute B (FB)

Product Points: Solute

Step 1) Find the mixing point M=F+S
Step 2) Determine mixing point compositions from
component material balances or inverse lever rule
Step 3) Since we know RN lies on the equilibrium
curve and we know (xA)RN we can determine (xB)RN and (xC)RN
Step 4) Since we know RN, M and E1 lie on a mixing
line we can locate E1 by extending a line from RN through
M to the equilibrium curve where it intersects E1. Plait Point
P
Extract
Feed
E1
Raffinate
M R1
Tie-lines
RN

Lecture 14: Hunter Nash Solvent C Carrier 6

 Liquid-Liquid Extraction: Operating Lines
E1 E2 E3 En En+1 EN-1 EN S Solvent C
Extract
1 2 n N–1 N
F RN-1 RN Raffinate
R1 R2 Rn-1 Rn RN-2
Carrier A (FA)
Solute B (FB)

Operating Points and Lines

Mass Balance around entire cascade: F  S  RN  E1

We define the operating point P as the F  E1  RN  S  P

difference between passing streams:

E1 E2 E3 En En+1 EN-1 EN S Solvent C

Extract
1 2 n N–1 N
F RN-1 RN Raffinate
R1 R2 Rn-1 Rn RN-2
Carrier A (FA)
Solute B (FB)

Mass Balance around the first n stages: F  En1  Rn  E1

We rearrange this equation to find that
all passing streams are related by the same F  E1  Rn  En1  P
operating point P.
Lecture 14: Hunter Nash 7
 The Operating Point
E1 E2 E3 En En+1 EN-1 EN S Solvent C
Extract
1 2 n N–1 N
F Rn RN-1 RN Raffinate
R1 R2 Rn-1 RN-2

Operating Points and Lines

Mass Balance around an internal stage: Rn  En  Rn1  En1
We can rearrange the above expression to
find that Rn is just a mixing point between Rn  Rn1  En  En1  P  En1
P and En+1.

The following figure illustrates this concept: En En+1 En+1

The stream Rn is the mixing point between Replace Rn-1 P
P and En+1 because P is the net flow into n and Enby P n
stage n from passing streams Rn-1, and En. Rn-1 Rn Rn

The N mass balances around the N individual F  E1  Rn1  En  RN  S  P

stages result in:

Extract
E2 E3 En En+1 EN-1 EN S
E1 Solvent C
1 2 n N–1 N
F Raffinate
R1 R2 Rn-1 Rn RN-2 RN-1
RN
Lecture 14: Hunter Nash 8
 Operating Lines
Operating Lines:
The raffinate points are mixing points between P and corresponding extract points. This is shown
graphically in the following diagram. Notice that to get the point P we need just F, S, E1 and RN.

Solute

E1
E2
F
E3 Operating Point
E4 R1
P
E5
E6 RN

S Carrier

Lecture 14: Hunter Nash 9

 Liquid-Liquid Extraction
E1 E2 E3 En En+1 EN-1 EN S Solvent C
Extract
1 2 n N–1 N
F RN-1 RN Raffinate
R1 R2 Rn-1 Rn RN-2
Carrier A (FA)
Solute B (FB)
Solute
Operating Points and Lines
Step 1) Locate the Operating Point by finding the intersection
of operating lines for the leftmost and rightmost stages
a) Draw a line through E1 and F
b) Draw a line through S and RN
c) Locate the intersection P. This point
is the operating point P.

Plait Point

E1
Feed
Operating Point
M P

RN

Lecture 14: Hunter Nash Carrier 10

 Liquid-Liquid Extraction
E1 E2 E3 En En+1 EN-1 EN S Solvent C
Extract
1 2 n N–1 N
F RN-1 RN Raffinate
R1 R2 Rn-1 Rn RN-2
Carrier A (FA)
Solute B (FB)
Solute

Operating Lines and Tie Lines: Stepping Off Stages:

Step 1) Locate point R1 from the tie line intersecting E1
Step 2) Draw a line from the operating point P through R1
to the extract side of the equilibrium curve.
The intersection locates E2.
Step 3) Locate point R2 from a tie line.
Plait Point Step 4) Repeat Steps 2 and 3 until RN is obtained.

E1
E2
Feed
E3 Operating Point
E4 R1
M P
E5
E6 RN
Carrier
Solvent C
Lecture 14: Hunter Nash 11
 Liquid-Liquid Extraction
E1 E2 E3 En En+1 EN-1 EN S Solvent C
Extract
1 2 n N–1 N
F RN-1 RN Raffinate
R1 R2 Rn-1 Rn RN-2
Carrier A (FA)
Solute B (FB)

Product Points:
Step 1) M=F+S
Step 2) Determine mixing point compositions from component material balances or inverse lever rule
Step 3) Since we know RN lies on a tie line and we know (xA)RN we can determine (xB)RN and (xC)RN
Step 4) Since we know RN, M and E1 lie on a mixing line we can locate E1 by extending a line from RN through
M to the equilibrium curve where it intersects E1.

Operating Points and Lines

Step 1) Locate the Operating Point by finding the intersection of operating lines for the leftmost
and rightmost stage
1a) Draw a line through E1 and F
1b) Draw a line through S and RN
1c) Locate the intersection P. This point is the operating point P.
Operating Lines and Tie Lines: Stepping Off Stages:
Step 1) Locate point R1 from the tie line intersecting E1
Step 2) Draw a line from the operating point P through R1 to the extract side of the equilibrium curve.
The intersection locates E2.
Step 3) Locate point R2 from a tie line.
Step 4) Repeat Steps 2 and 3 until RN is obtained.

Lecture 14: Hunter Nash 12

 Liquid-Liquid Extraction: Minimum Solvent

Operating Points and Lines

Step 1) Locate the raffinate Operating Line by extending
a line from S through RN
Step 2) Extend the tie lines to intersect the operating line
Step 3) The tie line that intersects furthest from RN
Solute gives the minimum operating point Pmin.
Step 4) Extend a line from Pmin through F to the extract side
of the equilibrium curve to find E1.
Step 5) Extend a line from E1 to RN. The intersection with the
line SF gives the minimum mixing point.

Note: If the tie lines slope down towards

the solvent side of the diagram, then
Plait Point the minimum operating point will lie on
the operating line at an intersection with
E1 a tie line nearest S.

Mmin

S RN Pmin

Mmax
Lecture 14: Hunter Nash Carrier 13
 Liquid-Liquid Extraction: Minimum Solvent

Solute
Stepping off Stages for the minimum solvent case
After locating the points Pmin, E1, and Mmin
the stages can be stepped off. If the minimum
solvent is used then the separation will be pinched
off and will require an infinite number of stages.

Plait Point

E1

Mmin

S Pmin
RN

Lecture 14: Hunter Nash Carrier 14

 Hunter Nash Liquid-Liquid Extraction

Today’s Lecture Covered:

Multistage Liquid-Liquid extraction

Specifications for liquid-liquid extraction cascades
Product points for a cascade
Operating lines and operating points
Hunter-Nash graphical construction
The Hunter-Nash Procedure
Stepping off stages
The minimum solvent solvent condition

Lecture 14: Hunter Nash 15