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LIQUID-LIQUID

EXTRACTION
MODELS/APPLICATIONS
EQUILIBRIUM RELATIONSHIPS


PHASE RULE FOR LLE


VARIABLES INCLUDED


PRESSURE


TEMPERATURE


4 COMPOSITIONS (2 IN EACH PHASE)
3 2 2 3
2 3
2
= + =
+ =
PHASES COMPONENTS FOR
P C
/
LLE DIAGRAMS -

FORMS


LLE CAN BE PRESENTED IN
VARIOUS FORMATS


TRIANGULAR, CARTESIAN,
McCABE-THIELE
Cehreli, S.; Bilgin, M,
.Quaternary Liquid-Liquid
Equilibrium of Water + Acetic
Acid + Propionic Acid + Solvent
(Amyl Alcohol, Cyclohexyl
Acetate, or Toluene) Systems,
J. Chem. Eng. Data; (Article);
2004; 49(5); 1456-1459.
OTHER LLE PLOTS
Kim, J .-K.; Park, D.-W., Liquid-Liquid Equilibrium for the
Quaternary System Toluene + Water + Propionic Acid + Ethyl
Acetate at 25 C and Atmospheric Pressure ,
J. Chem. Eng. Data; (Article); 2005; 50(2); 625-629
LLE PLOTS
Kim, J .-K.; Park, D.-W., Liquid-Liquid Equilibrium for the Quaternary
System Toluene + Water + Propionic Acid + Ethyl Acetate at 25 C
and Atmospheric Pressure ,
J. Chem. Eng. Data; (Article); 2005; 50(2); 625-629
LLE PLOTS


CARTESIAN SOLVENT-FREE PLOT
PERRYS Ed. 7, PAGE 15-7
SINGLE STAGE LLX MODELS


MASS BALANCES INCLUDE
OVERALL AND COMPONENT


NEED EQUILIBRIUM DATA TO
CALCULATE EQUILIBRIUM
CHANGES


STAGE EFFICIENCY LESS THAN
100% RESULTS IN A CHANGE IN
RELATIVE LOCATION OF x
a

VS x
a

*
EMPLOYS LEVER RULE
SINGLE STAGE LLX MODELS


TYPICAL MODEL FOR PROCESS:
Pandit, P.; Basu, S., Dye
and Solvent Recovery in
Solvent Extraction Using
Reverse Micelles for the
Removal of Ionic Dyes ,
Ind. Eng. Chem. Res.;
(Article); 2004; 43(24);
7861-7864.
MULTIPLE STAGE LLX MODELS


MODEL USES OVERALL AND
COMPONENT MASS BALANCES


EQUILIBRIUM DATA USED INITIALLY TO
DETERMINE MINIMUM SOLVENT (L/V)
RATIO (PONCHON-SAVARITT)


LOCATES y
a,min

ON EXTENDED EQUILIBRIUM
TIE LINE PASSING THROUGH x
a


USE LEVER RULE TO DETERMINE V
b,min


LOCALIZED EQUILIBRIUM VALUES CAN
RESULT IN ACTUAL V
b,min

VALUES BEING
HIGHER AND THIS WILL BE NOTICED IN
ACTUAL DESIGN IF Ncalc =
MULTIPLE STAGE LLX MODELS


SEQUENTIAL FEED

NORMALLY
COUNTERCURRENT
Nishihama, S.; Hirai, T.;
Komasawa, I., Separation and
Recovery of Gallium and
Indium from Simulated Zinc
Refinery Residue by Liquid-
Liquid Extraction ,
Ind. Eng. Chem. Res.;
(Article); 1999; 38(3); 1032-
1039.
MULTIPLE STAGE LLX MODELS


DESIGN IS BASED ON RATIO OF V
b,act

TO
V
b,min


USED TO LOCATE y
a,act


DESIGN POINT BASED IN INTERSECTION
OF x
a

-y
a

LINE WITH x
b

-y
b

LINE.


STAGES ARE STEPPED OFF BY
ALTERNATING BETWEEN
INTERSECTIONS ON EQUILIBRIUM
ENVELOPE DEFINED BY EQUILIBRIUM
TIE LINES AND LINES FROM DESIGN
POINT.
MULTIPLE STAGE LLX MODELS


McCABE THEILE DIAGRAM CAN BE
CONSTRUCTED FROM DATA FROM
PONCHON-SAVARITT


ALTERNATELY, IF B & S ARE
RELATIVELY IMMISCIBLE AND
FLOWS ARE SPECIFIED, THEN
INERT FLOW MODEL CAN BE USED
FOR THE OPERATING LINE. USING
COMPONENT BALANCES FOR
SOLUTE, A:
MULTIPLE STAGE LLX MODELS


INERT FLOWS MODEL


L' = NON-TRANSFERRING B IN
RAFFINATE AND V' = NON-

TRANSFERRING S IN EXTRACT.


CAN BE PLOTTED WITH EQUILIBRIUM
LINE ON McCABE-THIELE FOR
CALCULATIONS
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+
+
a
a
n
n
n
n
a
a
a
a
b
b
b
b
a
a
y
y
V
x
x
L
y
y
V
x
x
L
STAGE INTERIM FOR
y
y
V
x
x
L
y
y
V
x
x
L
OVERALL
1 1 1 1
1 1 1 1
1
1
` ` ` `
` ` ` `
LLX EQUIPMENT


MIXER-SETTLERS
A + B S
EXTRACT LAYER
RAFFINATE LAYER
EXTRACT
FAFFINATE
MIXER
SETTLER
LLX EQUIPMENT


SPRAY TYPE EXTRACTION TOWER
Chen, Liang-Huei (Chia-Nan Coll of Pharmacy and Science); Lee, Yuh-
Lang, Effects of a surfactant on the mass transfer in spray-tower
extraction column, Chemical Engineering Journal, v 73, n 1, 1999, p 77-
81
SPRAY TYPE EXTRACTION TOWER


USES A SPARGER FOR LIGHT
LIQUID AND DISPERSER FOR
HEAVY LIQUID


OVERFLOW IS LIGHT/UNDERFLOW
IS HEAVY
SIEVE TRAY EXTRACTION TOWER


SIMILAR TO DISTILLATION UNIT
J . Antonio Rocha, J . Carlos
Cardenas, Cesar Sosa, and J orge
Rosales, Preliminary design of
sieve tray extraction columns. 1.
Determination of the column
diameter. Flooding velocities in
sieve tray extractors , Ind. Eng.
Chem. Res.; 1989; 28(12) pp
1873 - 1878
SIEVE TRAY EXTRACTION TOWER


LIGHT LIQUID INVENTORIED
UNDER EACH TRAY


BUBBLES OF LIGHT LIQUID PASS
THROUGH COUNTERFLOW OF
HEAVY LIQUID


DOWNCOMERS ARE USED TO
TRANSFER HEAVY LIQUID DOWN
THE COLUMN
SIEVE TRAY EXTRACTION TOWER


DOWNCOMER DESIGN
J . Antonio Rocha, J . Carlos
Cardenas, Cesar Sosa, and
J orge Rosales, Preliminary
design of sieve tray extraction
columns. 1. Determination of the
column diameter. Flooding
velocities in sieve tray extractors
, Ind. Eng. Chem. Res.; 1989;
28(12) pp 1873 - 1878
YORK-SHEIBEL COLUMN


YORK-SHEIBEL COLUMNUSES
AGITATION TO MIX MATERIAL FOR
EACH STAGE WITH SETTLING
OCCURING OUTSIDE THE AGITATION
ZONE
PODBEILNIAK CENTRIFUGAL


PROVIDES A SINGLE STAGE HIGH
g CONTACTING
LIGHT OUT
LIGHT IN
HEAVY IN
HEAVY OUT
CONTACTING
REGIME
PROCESSES THAT UTILIZE LLX


TYPICALLY ARE THOSE IN WHICH
DISTILLATION IS NOT ECONOMICALLY
ATTRACTIVE


SULFOLANE PROCESS (UOP) -RECOVERY OF
AROMATICS, COMBINES DISTILLATION
WITH LLE
http://www.uop
.com/objects/5
5%20Sulfolane
.pdf
PROCESSES THAT UTILIZE LLX


BIOTECH AND BIOPHARM


SEPARATION OF HIGH MOLECULAR
WEIGHT FATTY ACIDS FROM
VEGETABLE OILS


PENICILLIN
Alfred Thomas, Fats and Fatty Oils,
Ullmann's Encyclopedia of Industrial
Chemistry
Copyright 2002 by Wiley-VCH Verlag
GmbH & Co. KGaA
PENICILLIN
PRODUCTION
PROCESS
J oseph A. Shaeiwitz,
J oseph D. Henry, J r.,
Biochemical Separations ,
Ullmann's Encyclopedia of
Industrial Chemistry
Copyright 2002 by
Wiley-VCH Verlag GmbH
& Co. KGaA
SUPERCRITICAL EXTRACTION


SOLVENT IS AT SUPERCRITICAL CONDITIONS


SUPERCRITICAL SOLVENT HAS
THERMODYNAMIC AND TRANSPORT
PROPERTIES THAT ARE SIMILAR TO A LOOSE
LIQUID OR A DENSE GAS.


SOLUTE EXTRACTION BASED ON SOLUBILITY IN
SUPERCRITICAL PHASE


PRODUCT IS OBTAINED BY LETTING PRESSURE
DOWN TO SUBCRITICAL CONDITIONS


PROCESS DESCRIBED IN TEXT DECAFFINATION
IS MORE LIKE SUPERCRITICAL LEACHING
TYPICAL SC PROCESS
Eldridge, R. B., Oil
Contaminant Removal
from Drill Cuttings by
Supercritical
Extraction, Ind. Eng.
Chem. Res.; (Article);
1996; 35(6); 1901-
1905.