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Liquid-liquid extraction

Basic principles
In liquid-liquid extraction, a soluble component (the solute) moves from one liquid phase to another. The two liquid phases must be either immiscible, or partially miscible. usually isothermal and isobaric can be done at low temperature (good for thermally fragile solutes, such as large organic molecules or biomolecules) can be very difficult to achieve good contact between poorly miscible liquids (low stage efficiency) extracting solvent is usually recycled, often by distillation (expensive and energy-intensive)

can be single stage (mixer-settler) or multistage (cascade)

Extraction equipment
Batch: Continuous: single-stage: column:

separatory funnel

mixer-settler rotating-disk contacter a. agitator; b. stator disk


Mixer-settlers, both as stand-alone and as incolumn type, are offered for special applications. As implied by the name, the mixer-settler-column is a series of mixersettlers in the form of a column. It consists of a number of stages installed one on top of the Mixer-settlers operate with a purely stageother, eachis hydraulically separated, and each wise contact. After every mixer there a with a mixing ettler. Mixer-settlers can be operated inand a settling zone (see below). This design enables the elimination of some of multistage, co- or countercurrent fashion. the main disadvantages of conventional mixersettlers, whilst maintaining stage-wise phase contact. The mechanical design of the mixer-settlercolumn is comparable to the agitated ECR Khni column. Key characteristics For long residence times: >15 min Extraction controlled by residence time Reactive extraction systems Long phase separation For extraction controlled by pH (stage-wise pH adjustment)

Mixer-settler column


Separation of high-boiling products or pollutants that are present in only low concentrations Separation of components with similar boiling points or components forming ction with high mass transfer and/or azeotropes ng physical properties, this is the Separation of mixtures with of choice. The geometry of the thermally sensitive components d compartments can be adapted for Selective separation of single ng hydrodynamic conditions. Other components out of a complex mixture atures are the special mixing turbines Our portfolio includes a complete range of perforated partition plates. liquid-liquid-extraction equipment, enabling us to provide you with the most appropriate solution for your requirements. In addition to agitated columns, it includes mixer-settlers and packed columns. Design The agitated Khni column has a simple and robust design. The drive unit and the shaft are supported at the top of the column, allowing you to use all common types of shaft seals (stuffing box, mechanical seals). In special cases, the seal can be replaced by a magnetic drive. Only radial slide-bearings are necessary

Agitated column

Packed extraction column

The ECP packed column is based on c Packing The special Sulzer extraction packing Liquid distributors In order to create an even liquid flow Main benefits High specific throughput fac Small column diameters Revamp of existing columns Use in cases of difficult phy Low density difference < 50 Low interfacial tension: < 2 Tendency to form emulsion Reliable scale-up

Stream labeling
feed solvent mixer mixture settler raffinate extract E, yA,1 1 F, xA,0

Feed (F) contains solute A (xA) dissolved in diluent D (xD = 1 xA).

SE solvent flow rate Solvent (S) extracts A (yA), creating the product = FS = constant

FR diluent flow rate = FD = constant

extract stream (E). The depleted feed becomes the product raffinate stream (R).
Equilibrium (no longer VLE!) is defined by the distribution ratio, Kd:
S, yA,N+1 N R, xA,N

Kd = yA/xA Note that yA does not refer to gas composition. Usually specified: yA,N+1, xA,0, FD/FS and xA,N.

McCabe-Thiele analysis: Counter-current extraction with immiscible liquids

Equation of the operating line:
FD FD Y= X + (Y1 X ) FS FS 0

(analogous to operating line for stripper column). (FD/FS)max gives FS,min for N = .
2 3



For dilute solutions,

R R y = x + (y1 - x0 ) E E Can also use Kremser eqns, if solutions are dilute and equil. line is straight.
mE y N +1 - y 0 mE ln 1 + R y y R 1 0 N= ln R mE

N=3 (XN,YN+1)

Cross-flow cascade
From mass balance around stage j:

R R y j = - xi + (y j ,in + x j -1) Ej Ej

Figure 13-8 Cross-flow cascade

From Separation Process Engineering, Third Edition by Phillip C. Wankat (ISBN: 0131382276) Copyright 2012 Pearson Education, Inc. All rights reserved.


Increase overall efficiency by introducing fresh extracting solvent at each stage. Each stage has its own mass balance and operating line
(x2,y2) (x3,y3)


Uses much more solvent than countercurrent cascade (requires much more solvent recovery)
A mixer-settler is just one cross-flow stage.




Dilute fractional extraction

A common situation: the feed contains two important solutes (A, B), and we want to separate them from each other. Choose two solvents: A prefers solvent 1 (extract) B prefers solvent 2 (raffinate)
F zA zB extract yA,1 yB,1 1 solvent 2 xA,0 = 0 xB,0 = 0 absorbing section stripping section


Kd,A = yA/xA > 1

Kd,B = yB/xB < 1

solvent 1 yA,N+1 = 0 yB,N+1 = 0

raffinate xA,N xB,N

McCabe-Thiele analysis: dilute fractional extraction

One operating line for each solute i, in each section of the column (i.e., 4 total). Top operating lines (absorbing section): R R yi = xi + (yi,1 - xi,0 ) E E Bottom operating lines (stripping section):
R R y i = xi + (y i ,1 - xi ,0 ) E E

Operating lines intersect at feed composition (not shown, may be very large).

3 5 yA,1 1 6

N = 4, F feed stage

Equilibrium data is different for each solute (use separate McCabe-Thiele diagrams!)
If yA,1 and xA,N are specified, and NF is known, use M-T diagram to obtain N, then use trial-and-error to find xB,0 and xB,N+1

xA,N If yA,1 and xB,N are specified, vary NF (trial-and-error) until N is the same for both solutes.

Center-cut extraction
When there are 3 solutes: A, B and C, and B is desired (A and C may be > 1 component each) Requires two columns: column 1 separates A from B+C column 2 separates B from C Requires three extracting solvents: A prefers solvent 1 over solvent 2 B, C prefer solvent 2 over solvent 1 B prefers solvent 3 over solvent 2 C prefers solvent 2 over solvent 3 solvent 1 +A solvent 2

solvent 3 +B

solvent 2

F zA, zB, zC

solvent 1

solvent 2 +B+C

solvent 3

solvent 2 +C

Partially miscible solvents

There are two liquid phases Each phase is a ternary (3-component) mixture of solute A, diluent D and solvent S Ternary equilibrium diagrams have 3 axes: usually, mole or mass fractions of A, D, and S Literature data is commonly presently on an equilateral triangle diagram (note NO origin) Each axis is bounded 0 x 1 Miscibility boundary = equilibrium line (depends on T, P)

Figure 13-14 Effect of temperature on equilibrium of methylcyclohexane-toluene-ammonia system from Fenske et al., AIChE Journal, 1,335 (1955), 1955, AIChE
From Separation Process Engineering, Third Edition by Phillip C. Wankat (ISBN: 0131382276) 2012 Pearson Education, Inc. All rights reserved.

Reading ternary phase diagrams

Consider the point M: water content (xA) is ? 0.19 ethylene glycol content (xB) is ? 0.20 furfural content (xC) is ? 0.61

check: xA + xB + xC = 1
Read the mole/mass fraction of each component on the axis for that component, using the lines parallel to the edge opposite the corner corresponding to the pure component.

The mixture M lies inside the miscibility boundary, and will spontaneously separate into two phases. Their compositions (E and R) are given by the tie-line through M. region of partial miscibility A-C The compositions of E and R converge at the plait point, P (i.e., no separation).
A 2-component mixture of furfural and water is partially miscible over the composition range from about 8 % furfural to 95 % furfural. Separation by extraction requires a furfural/water ratio in this range (otherwise single phase).

Right-triangle phase diagrams

Raffinate (diluent-rich): xA + xB + xC = 1 Extract (solvent-rich): yA + yB + yC = 1

We need to specify only two of the compositions in order to describe each liquid phase completely .
This can be shown on a right-triangle phase diagram, which is easy to plot and read. raffinate compositions are represented by coordinates (xA, xB) extract compositions are represented by coordinates (yA, yB)
Vertical axis corresponds to both xA and yA. Horizontal axis corresponds to both xB and yB
Q: Where does pure C appear on this diagram?

Figure 13-12 Equilibrium for water-chloroform-acetone at 25C and 1 atm From Separation Process Engineering, Third Edition by Phillip C. Wankat (ISBN: 0131382276) Copyright 2012 Pearson Education, Inc. All rights reserved.

More tie-lines can be obtained by trial-anderror, using the conjugate line. Ex.: find the tie-line that passes through M.

Obtaining the conjugate line

Each point on the conjugate line is composed of - one coordinate from the extract side of the equilibrium line - one coordinate from the raffinate side of the equilibrium line

On this graph, which component is the diluent? which is the solute?

Hunter-Nash analysis of mixer-settler

F S mixer M settler R E Why does F appear on or near the hypotenuse?

Flow rates of E and R are related by mass balance. Compositions of E and R are also related by equilibrium.
Overview of solution using RT diagram: 1. Plot F and S and join with a line. 2. Find mixing point, M, which is co-linear with F and S. 3. Find tie-line through M; find E and R at either end (colinear with M). 4. Find flow rates of E and R.

coord.: (yD,yA)
mixing line

Why does S appear at or near the origin?

F E M tie-line S

coord.: (xD,xA) R

F S mixer solve for coordinates of M: (xA,M, xD,M) M

Why are F, S and M co-linear on the Hunter-Nash diagram?


xA,M = xD,M =
xA,M - xA,S xD,M - xD ,S =

FxA,F + SxA,S F +S FxD,F + SxD,S F +S

xA,F - xA,M xD,F - xD,M

CMBA: FxA,F + SxA,S = MxA,M = (F + S)xA,M CMBD: FxD,F + SxD,S = MxD,M = (F + S)xD,M
F xA,M - xA,S xD ,M - xD,S = = S xA,F - xA,M xD,F - xD,M


F (xD,F, xA,F) M (xD,M, xA,M) S (xD,S ,xA,S)

slope from slope from M to S F to M

Therefore F, S and M are co-linear. To locate M on the FS line: calculate either xA,M or xD,M.

The lever-arm rule

Another way to locate M: To calculate flow rates E and R:




similar triangles

similar triangles


FxA,F + SxA,S = MxA,M FxA,F + (M F)xA,S = MxA,M

R xA,M - y A,E ME = = M xA,R - y A,E RE

F(xA,F - xA,S) = M(xA,M - xA,S)

F xA,M - xA,S MS = = M xA,F - xA,S FS

Your choice! Use mass balances, or measure distances and use lever-arm rule.

Hunter-Nash analysis of cross-flow cascade

S1 F = R0 1 E1 R1 S2 2 E1 F M1 E2 M2 R2

Treat each stage as a mixer-settler.


each Ri, Si pair creates a mixing line find each Ei, Ri pair using a tie-line

R1 R2

Hunter-Nash analysis of counter-current cascade

F S mixer M separator (column) R1 EN

E and R are both points on the equilibrium line. But they are not related by the same tie-line.

Overview of solution using RT diagram: 1. Plot F and S and join with a line. 2. Find mixing point, M, which is colinear with F and S. 3. Plot specified xA,1 on raffinate side of equilibrium line to find R1. 4. Extrapolate R1M line to find EN. 5. Find flow rates of E and R.

mixing line

EN xA,1

M NOT a tie-line


Stage-by-stage analysis
R1 xA,1 1 R2 E1 S = E0 yA,0

stage 1 TMB:

E 0 + R2 = E 1 + R1 E0 R1 = E1 R2 = E2 R3 etc.

constant difference in flow rates of passing streams = Ej Rj+1 = constant stage 1 CMBA: E0yA,0 + R2xA,2 = E1yA,1 + R1xA,1 E0yA,0 R1xA,1 = E1yA,1 R2xA,2 = etc.

F = RN+1 xA,N+1

EN yA,N+1

constant difference in compositions of passing streams net flow of A: xA, = EjyA,j Rj+1xA,j+1 net flow of D: xD, = EjyD,j Rj+1xD,j+1

The difference point

Define a difference point, , with coordinates (xA, , xD, ):
xA,D = E0 y A,0 - R1xA,1 D xD,D = E0 y D,0 - R1xD ,1 D

does not necessarily lie inside the RT graph. All pairs of passing streams Ej, Rj+1 are co-linear with . Using the -point to step off stages on Hunter-Nash diagram: using the specified location of R1 (as xA,1), can find E1 (use tie-line); given the location of E1, can find R2 (use ); given the location of R2, can find E2 (use tie-line); given the location of E2, can find R3 (use ); and so on, until desired separation is achieved.

First, need to locate . It may be on either side of the Hunter-Nash diagram.

Finding the -point

Procedure: 1. Plot F (= RN+1), S = (E0). Locate M. 2. Plot R1 and locate EN. 3. Extend the lines joining E0-R1, and EN-RN+1, to find at the intersection point.

last mixing line EN F = RN+1


first mixing line

S = E0

4. All intermediate mixing lines must pass through .

Stepping off stages on the H-N diagram

Procedure: N=3 1. Use R1 and conjugate line to find E1 2. Use E1 and D-point to find R2 3. Use R2 and conjugate line to find E2 4. Use E2 and D-point to find R3 EN E2 E1 S = E0 3. Use R3 and conjugate line to find E3 F = RN+1 R3


R1 Stop when you reach or pass EN.

Using McCabe-Thiele diagram instead of Hunter-Nash

M-T diagram can be used with much greater accuracy than H-N diagram Need to transfer ternary equilibrium data from RT diagram Need to obtain the operating line
Transferring equilibrium data from RT diagram Each tie-line represents a pair of equilibrium streams extract composition represented by yA raffinate composition represented by xA Each (xA, yA) pair is a point on the M-T equilibrium line
raffinate compositions

extract compositions

A yA xA

1 0 0 xA

equilibrium line ends at P

yA 1

0 0

Obtaining the M-T operating line

R1 xA,1 1 S = E0 yA,0 A xN+1 x1 y0 E0

Mixing lines represent passing streams. All mixing lines lie between the limits: (x1, y0) and (xN+1, yN)


WAIT! In general, operating line is not straight. Plot arbitrary intermediate mixing lines to obtain more points. 1

N F = RN+1 xA,N+1 EN yA,N+1

yA xA

(xN+1, yN)

Note: passing streams are (xj+1, yj) instead of (xj, yj+1) as in distillation, simply due to our labeling convention (feed enters at stage N).

0 0 (x1, y0)

Choice of extracting solvent flow rate

As S increases, separation improves, but extract becomes more dilute As S decreases, N must increase to maintain desired separation Smin achieves the desired separation with N = as M moves towards S, (S/F) increases (lever-arm rule) when M reaches the equilibrium line, all feed dissolves in extracting solvent (Mmax)

A F M Mmin S Mmax D

as M moves towards F, (S/F) decreases before reaching the equilibrium line, there is usually a pinch point (Mmin)

It is not easy to locate this pinch point on a McCabe-Thiele diagram, since the operating line curvature changes as S changes. On a Hunter-Nash diagram, Dmin (corresponding to Mmin) occurs when a mixing line and a tie-line coincide.

Minimum solvent flow rate

On H-N diagram whose tie-lines have negative slopes: Plot S = E0, F = RN+1, R1 Join S and F Extend SR1 mixing line Locate several tie-lines Extend tie-lines to the SR1 mixing line 6. Tie-line with furthest intersection from S locates Dmin 7. Mixing line from Dmin through F locates EN,min 1. 2. 3. 4. 5.


10. (S/F)min = (FMmin)/(SMmin) Rule-of-thumb: (S/F)act ~ 1.5 (S/F)min


8. Connecting R1 and EN,min completes the mass balance 9. Mmin is located at the intersection of SF and R1EN,min

Minimum solvent flow rate

On H-N diagram whose tie-lines have positive slopes: Strategy: 1. Plot S = E0, F = RN+1, R1 2. Join S and F 3. Extend SR1 mixing line 4. Locate several tie-lines 5. Extend tie-lines to SR1 mixing line 6. Find tie-line which gives closest intersection to S; this locates Dmin 7. Draw mixing line from Dmin through F to locate EN,min 8. Connect R1 and EN,min to complete mass balance



9. Mmin is at the intersection of SF and R1EN,min 10. (S/F)min = (FMmin)/(SMmin)


Two feed counter-current column

S R1 1 E0 = S F1 M mixer 2 separator R1 EN

mixer 1



Feed balance: F1 + F2 = FT

N F1 = RN+1

Overall balance: hypothetical mixed feedstream FT is co-linear with F1, F2


Stage-by-stage analysis: mass balance changes where F2 enters the column upper and lower sections have different sets of operating lines different D-points

Hunter-Nash analysis of 2-feed column

Overall balance: 1. Plot F1 and F2. Locate FT (colinear with F1 and F2). 2. Plot S . Locate M (co-linear with S and FT). FT F2 R1 3. Plot R1. Locate EN (co-linear with R1 and M). 1. Calculate flow rates R1 and EN.


S = E0

Stage-by-stage analysis
R1 1 j R F2 k E E0 = S Balance around top of column: R1 E0 = Rj+1 Ej = D1 linear R1, E0, D1 are co-

Balance around bottom of column: EN RN+1 = Ek Rk+1 = D2 RN+1, EN, D2 are co-linear
Overall balance: F2 + RN+1 + E0 = EN + R1 F2 = (EN RN+1) + (R1 E0) = D1 + D2 F2, D1, D2 are co-linear feed-line

N F1 = RN+1

D2 is located at the intersection of two mixing lines: RN+1, EN, D2 and F2 , D 1 , D 2 Need another line to locate D1: TMB: FT = F1 + F2 = EN + (R1 E0) = EN + D1 FT, EN, D1 are co-linear D1 is located at the intersection of two mixing lines: R1, E0, D1 and FT, EN, D2


Note: D1 and D2 may be on different sides of the phase diagram.

Using the feed-line

1. Locate D1 at intersection of R1E0 and ENFT 2. Locate D2 at intersection of F2D1 and ENRN+1

3. Step off stages, initially using D1 to generate the first mixing lines



5. When the tie-line crosses the feed line, the next mixing line will be generated using D2



E2 E1


F1 FT F2

4. Identify the optimum feed stage when the mixing line crosses the feed line, F2D1D2
feed line

Countercurrent liquid-liquid extraction with reflux

R1 1 E0 = S

How to increase yA,N? need to increase xA,N+1 make RN+1 an reflux stream

makeup solvent

R1 1


extract reflux
(no benefit to raffinate reflux)

Turning extract into raffinate : extract is mostly solvent raffinate is mostly diluent We need to remove solvent, e.g., distillation, stripping

N RN+1

recovered solvent

N F1 = RN+1 xA,N+1


solvent separator

In a conventional liquid-liquid extraction column: reflux yA,N is related by equilibrium to xA,N xA,N depends on xA,N+1 dilute feed gives dilute extract highest yA,N obtained with S Smin , but this requires very large N


product extract

Analogy to distillation reflux


L0 D RN+1 Saturated liquid reflux stream is obtained by condensing V1 (vapor stream rich in A) to give L0 (liquid stream rich in A) External reflux ratio = L0/D Internal reflux ratio = L/V


recovered solvent

solvent separator


product extract

Extract reflux stream is obtained by removing solvent from EN (extract stream rich in A and solvent) to give RN+1 (raffinate stream rich in A and depleted in solvent) External reflux ratio = RN+1/PE Internal reflux ratio = RN+1/EN

Stage-by-stage balances
Similar to 2-feed liq-liq extraction column: - two D-points (mass balance above and below feed stage) - if F, E0, R1 and RN+1 are specified, same stage-by-stage analysis But RN+1 is an internal stream, usually not specified. Usually specified: F, xA,F, xD,F yA,0, yD,0 xA,1 xA,PE, xD,PE rates) yA,SR, yD,SR RN+1/PE

plot F plot E0 plot R1 on satd raffinate curve plot PE (same location as RN+1 and Q, different flow plot SR

Mass balance: solvent separator

solvent separator

EN = Q + SR = RN+1 + PE + SR
PE A EN SR E0 PE, Q, RN+1 F R1 D

EN is co-linear with Q and SR. EN also lies on satd extract line. Obtain EN/SR from lever-arm rule. We will also need RN+1/SR:
EN RN +1 PE = + +1 SR SR SR dont know

EN SR RN +1 S = + 1+ R SR PE PE PE

RN +1 +1 PE R E P SR N +1 = N - E - 1 = SR SR SR EN PE 1 SR

Finding the D-points

D2 = EN - RN+1 D2xA,D2 = ENyA,N - RN+1xA,N+1
xA,D 2 = EN y A,N - RN +1xA,N +1 EN - RN +1

We dont know the individual flow rates EN, RN+1, but we know EN/SR and RN+1/SR. We can calculate xA,D2 and thereby locate D2 on the ENRN+1 line.


Locate D1 at the intersection D2 of two mixing lines: D1 = E0 - R1 D1 F = D1 + D2

Proceed to step off stages.