# LIQUID-LIQUID EXTRACTION • • • • • • • • • • Overview Examples of liquid-liquid extraction Solvent selectivity Partition coefficient Types of ternary system

Simple equilibrium stage Solvent-free basis Simple multiple extraction Countercurrent Multistage Extraction  Ponchon-Savarit method  McCabe-Thiele method Minimum solvent-to-feed ratio

Overview Liquid-liquid extraction is a separation process in which a component in a solution is removed with the use of a solvent. The desired component in solution is called the solute (A), mixed with the less desired component called the diluent (B). Solvent (C) is added as separating agent. The solute is partitioned between two immiscible liquid phases. Components C and B may either be immiscible or partially miscible. The solute is partitioned between two immiscible liquid phases: the extract (V) phase, which is rich in solvent, and the raffinate (L) phase, which is rich in diluent. Examples of liquid-liquid extraction • • Separation of penicillin from its fermentation mixtures Removal of acetic acid from water using organic solvent

Solvent selectivity The ability of solvent to pick up desired component in feed relative to other components.
α= yA yB xA xB

where y = extract concentration x = raffinate concentration If α = 1.0, there is no separation of the components between two liquid phases. Partition coefficient Distribution (or partition) coefficient for component A is defined as the ratio of concentration of A in extract phase to that in raffinate phase; solubility should be high so that the ratio of solvent to feed is low.
K= yA xA

where K = distribution coefficient In solvent-free basis, the partition coefficient may be defined as

K′ =

YA XA

If raffinate and extract phases are completely immiscible, K is greater than 1, denoting that less solvent is required. In single stage equilibrium, K, can be used to determine the composition of solute in the two phases.
K= y A1 L1  L 0 x A 0  = − 1  x A1 V1  L1 x A1 

where L0 = mass of feed L1 = mass of raffinate V1 = mass of extract x A 0 = mass fraction of solute in feed x A1 = mass fraction of solute in raffinate y A 2 = mass fraction of solute in solvent = 0 y A1 = mass fraction of solute in extract Types of ternary systems Depending on the type of liquid ternary system, mixing of three components may result in either one phase or two phases. The figure below represents a system (Type I) in which one pair of liquids is partially miscible (B and C). Type II system, represented below, has two pairs of partially miscible liquids (B-C and A-C). In this Type II system, there is no plait point. C C

B Type I system

A

B Type II system

A

Simple equilibrium stage If feed, L0, and solvent, V2, are mixed, the resultant mixture, Σ , has two liquid phases (extract, V1 and raffinate, L1), the compositions (x, y) of which may be determined by the use of ternary diagram. V1, yA1, yB1, yC1 L0, xA0, xB0, xC0 Σ , zA, zB, zC V2, yA2, yB2, yC2 L1, xA1, xB1, xC1

Note: For composition, first or letter subscript denotes component and second or number subscript denotes equilibrium stage.
L 0 + V2 = Σ Total balance: Component A balance: L 0 x A 0 + V2 y A 2 = Σz A Component C L x + V y = Σz 0 C0 2 C2 C balance:

Component B balance is not included since summation of mass fractions equals 1. Solvent-free basis Ternary liquid system Type II is inconveniently short for stage calculation, so it can be transformed to solvent-free basis. The notation and relationship are redefined as: L’ = mass of two components A and B, disregarding the solvent C in phase L V’ = mass of two components A and B, disregarding the solvent C in phase V X = mass of any component A, B, or C per unit mass of L’ Y = mass of any component A, B, or C per unit mass of V’ With this notation,
X A + XB = 1 , Xc can have a value >1 YA + YB = 1, Yc can have a value >1

Simple multiple extraction Simple multiple extraction refers to the use fresh solvent, V0, in each equilibrium stage. The number of theoretical stages can be determined graphically. The procedure is to locate the resultant mixture, Σ , then the composition of the resulting phases can be located using the equilibrium curve with the aid of the tie-line. The resulting raffinate phase is then mixed with a fresh batch of solvent to produce the second Σ in the next stage. The step is repeated until the Nth stage is reached. V0 L1 V0 L2 V0

L0

1

2

3

L3

V1

V2

V3

For solvent-free basis, the number of theoretical equilibrium stages can be computed as follows:

XA0 X AN N= V' log( K ' ' 0 + 1) L0 log
where
' V0 L'0 = ratio of solvent to feed

YA0 = mass of solute in solvent = 0 XA0 = mass fraction of solute in feed XAN = mass fraction of solute in final raffinate phase Countercurrent multistage extraction V1 L0 Ponchon-Savarit method The method makes use of the delta, ∆ , to relate streams flowing past each other in opposite direction. It is a fictitious stream; thereby a net flow in the difference between the two streams. This is useful in the stage-to-stage calculation. Total mass balance: L0 + Vn+1 = Σ = V1 + Ln ∆ = L0 – V1 = Ln - Vn+1 V2 1 L1 2 ∆ N VN+1 LN

In making use of the delta to determine the number of theoretical equilibrium stages, Σ is first located using the inverse lever arm rule. Once all the end streams are located graphically, the net flow, ∆ , is then determined. Stages are computed in a stepwise manner alternating from the equilibrium curve to delta until the composition in the final raffinate stage is reached. D

Sn+1

1.0 0.9 0.8 0.7 0.6 0.5 0.4 1 0.3 0.9 0.2 0.8 0.1 0.7 0.0 0.6 0.5 0.4 0.3 0.2 0.1 0 0 0.1 0.2 0.3 0.4 0.5 0.6 0.7 0.8 0.9 1
L0 Sn+1 S1

Ln

L0

0.0 0.1 0.2 0.3 0.4 0.5 0.6 0.7 0.8 0.9 1.0

Note: If N (number of stages) is given, the solution is trial and error.

McCabe-Thiele method In this method of determining the number of theoretical equilibrium stages, the operating line replaces the delta. This is specifically applicable when the two components (B and C) are completely immiscible. The operating line is given by the equation: Yn +1 = L' V ' Y1 − L' X0 Xn + V' V'

To yield a straight operating line, the mass fraction is changed to mass ratio. The variables are redefined as: V’ = mass of solvent C, not including solute A L’ = mass of unextracted component B, not including solute A Y = mass of solute A per unit mass of solvent C in extract phase X = mass of solute A per unit mass of unextracted component B in raffinate phase Rearranging:
L' Y − Y1 = n +1 V' Xn − X 0

If 4 streams are given or 3 streams and the V/L ratio are given, the operating line can be plotted with the equilibrium curve (replotted in mass ratio). The number of stages may be determined by stepping-down in a “staircase” manner.

Equilibrium curve

YA mass ratio, mass A/mass C

YA1 XA2 XA3 XA4

XA1

YA2 YA3

Operating Line

YA4

YN+1 XN

XA0

XA mass ratio, mass A/massB

Minimum solvent-to-feed ratio (For a process with a component that is insoluble in the solvent). Conditions are that there is no solvent in the feed, x 0 A = 0 , and if the solvent is pure, x n +1,S = 1.

P = (1 − L n )

x1S x nS Ln 1 1 − x S 1S 1 − x1S

where P = solvent to feed ratio, Vn+1/L0 minimum P occurs for x1S = 0 References Das, D.K. and R.K. Prabhudesai. 1999. Chemical Engineering License Review. 2nd edition. Engineering Press. Austin, Texas. Crokett, William E. 1986. Chemical Engineering. A Review for the P.E. Exam. John Wiley & Sons, Inc. New York. Foust, Alan S., L.A. Wenzel, C.W. Clamp, L. Maus, and L.B. Andersen. 1980. Principles of Unit Operations. 2nd ed. John Wiley & Sons, New York. Perry, Robert H. and D.W. Green. 2001. Perry’s Chemical Engineers’ Handbook. 7 th edition. McGraw-Hill. Singapore.