14
EXTRACTION AND LEACHING
E xtraction is a process whereby a mixture of several
substances in the liquid phase is at least partially
separated upon addition of a liquid solvent in which the
original substances have different solubilities.
When some of the original substances are solids, the
process is called leaching. In a sense, the role of solvent in
extraction is analogous to the role of enthalpy in distillation.
The solvent-rich phase is called the extract, and the solvent-
poor phase is called the raffinate. A high degree of
separation may be achieved with several extraction stages in
series, particularly in countercurrent flow.
Processes of separation by extraction, distillation,
crystallization,or adsorption sometimes are equally possible.
Differences in solubility, and hence of separability by
extraction, are associated with differences in chemical
structure, whereas differences in vapor pressure are the
basis of separation by distillation. Extraction often is effective
at near-ambient temperatures, a valuable feature in the
separation of thermally unstable natural mixtures or
pharmaceutical substances such as penicillin.
The simplest separation by extraction involves two
substances and a solvent. Equilibria in such cases are
represented conveniently on triangular diagrams, either
equilateral or right-angled,as for example on Figures 14.1 and
14.2. Equivalent representations on rectangular coordinates
also are shown. Equilibria between any number of substances
are representable in terms of activity coefficient correlations
such as the UNlQUAC or NRTL. In theory, these correlations
involve only parameters that are derivable from
measurements on binary mixtures, but in practice the
resulting accuracy may be poor and some multicomponent
equilibrium measurements also should be used to find the
parameters. Finding the parameters of these equations is a
complex enough operation to require the use of a computer.
An extensive compilation of equilibrium diagrams and
UNlQUAC and NRTL parameters is that of Sorensen and Ark
(1979- 1980).Extensive bibliographies have been compiled by
Wisniak and Tamir (1980- 198 1).
The highest degree of separation with a minimum of
14.1. EQUILIBRIUM RELATIONS
On a ternary equilibrium diagram like that of Figure 14.1, the limits of
mutual solubilities are marked by the binodal curve and the compositions
of phases in equilibrium by tielines. The region within the dome is two-
phase and that outside is one-phase. The most common systems are those
with one pair (Type I, Fig. 14.1) and two pairs (Type 11, Fig. 14.4) of
partially miscible substances. For instance, of the approximately lo00 sets
of data collected and analyzed by Sorensen and Arlt (1979), 75% are Type
I and 20% are Type 11. The remaining small percentage of systems
exhibit a considerable variety of behaviors, a few of which appear in
Figure 14.4. As some of these examples show, the effect of temperature
on phase behavior of liquids often is very pronounced.
Both equilateral and right triangular diagrams have the property
that the compositions of mixtures of all proportions of two mixtures
appear on the straight line connecting the original
459
solvent is attained with a series of countercurrent stages.
Such an assembly of mixing and separating equipment is
represented in Figure 14.3(a).and more schematically in
Figure 14.3(b).In the laboratory, the performance of a
continuous countercurrent extractor can be simulated with a
series of batch operations in separatov funnels, as in Figure
14.3(c).As the number of operations increases horizontally,
the terminal concentrations E, and R3 approach
asymptotically those obtained in continuous equipment.
Various kinds of more sophisticated continuous equipment
also are widely used in laboratories; some are described by
Lo et a/. (1983, pp, 497-506). Laboratory work is of particular
importance for complex mixtures whose equilibrium relations
are not known and for which stage requirements cannot be
calculated.
In mixer-separators the contact times can be made long
enough for any desired approach to equilibrium, but 80-90%
efficiencies are economically justifiable. If five stages are
required to duplicate the performance of four equilibrium
stages, the stage efficiency is 80%. Since mixer-separator
assemblies take much floor space, they usually are
employed in batteries of at most four or five units. A large
variety of more compact equipment is being used. The
simplest in concept are various kinds of tower arrangements.
The relations between their dimensions, the operating
conditions, and the equivalent number of stages are the key
information.
Calculations of the relations between the input and
output amounts and compositions and the number of
extraction stages are based on material balances and
equilibrium relations. Knowledge of efficiencies and
capacities of the equipment then is applied to find its
actual size and configuration. Since extraction processes
usually are performed under adiabatic and isothermal
conditions, in this respect the design problem is simpler
than for thermal separations where enthalpy balances
also are involved. On the other hand, the design is
complicated by the fact that extraction is feasible only of
nonideal liquid mixtures. Consequently, the activity
coefficient behaviors of two liquid phases must be taken
into account or direct equilibrium data must be available.
mixtures. Moreover, the relative amounts of the original mixtures
corresponding to an overall composition may be found from ratios of
Line segments. Thus, on the figure of Example 14.2, the amounts of
extract and raffinate corresponding to an overall composition M are in the
ratio E , / R N = M R N / E , M .
Experimental data on only 26 quaternary systems were found by
Sorensen and Arlt (1979), and none of more complex systems,
although a few scattered measurements do appear in the literature.
Graphical representation of quaternary systems is possible but
awkward, so that their behavior usually is analyzed with equations.
To a limited degree of accuracy, the phase behavior of complex
mixtures can be predicted from measurements on binary mixtures,
and considerably better when some ternary measurements also are
available. The data are correlated as activity coefficients by means of
the UNIQUAC or NRTL equations. The basic principle of application
is that at equilibrium the activity of each component is the same in
both phases. In terms of activity coefficients this
 460 EXTRAC
TION AND
LEACHING

A
C
Solute

-k-P
G
A-rich
+

s.
m

qpT\ locus

50
0
$- 40

r 30
20
10

p,
C I (A + C), A-rich phase
(C)
Figure 14.1. Equilibria in a ternary system, type 1, with one pair of partially miscible liquids; A = 1-
hexene, B = tetramethylene sulfone, C = benzene, at 50C (R . M . De Fre, thesis, Gent, 1976).
(a) Equilateral triangular plot; point P is at 20% A, 10% B, and 70% C. (b) Right triangular plot with
tielines and tieline locus, the amount of A can be read off along the perpendicular to the hypotenuse or by
difference. (c) Rectangular coordinate plot with tieline correlation below, also called Janecke and solvent-
free coordinates.

condition is for component i, Compositions of petroleum mixtures sometimes are repre-sented

YJ, = y:x:,
where * designates the second phase. This may be rearranged into a
relation of distributions of compositions between the phases,
xt = ( Y , / Y : ) ~ ,= K,x,,
where K,is the distribution coefficient. The activity coefficients are
functions of the composition of the mixture and the temperature.
Applications to the calculation of stage requirements for extraction
are described later.
Extraction behavior of highly complex mixtures usually can be
known only from experiment. The simplest equipment for that
purpose is the separatory funnel, but complex operations can be
simulated with proper procedures, for instance, as in Figure 14.3(c).
Elaborate automatic laboratory equipment is in use. One of them
employs a 10,000-25,000rpm mixer with a residence time of 0.3-5.0
sec, followed by a highly efficient centrifuge and two
chromatographs for analysis of the two phases (Lo et al., 1983, pp.
507).
adequately in terms of some physical property. Three examples
appear in Figure 14.5. Straight line combining of mixtures still is
valid on such diagrams.
Basically, compositions of phases in equilibrium are indicated
with tielines. For convenience of interpolation and to reduce the
clutter, however, various kinds of tieline loci may be constructed,
usually as loci of intersections of projections from the two ends of the
tielines. In Figure 14.1 the projections are parallel to the base and to
the hypotenuse, whereas in Figures 14.2 and 14.6 they are horizontal
and vertical.
Several tieline correlations in equation form have been
proposed, of which three may be presented. They are expressed in
weight fractions identified with these subscripts:
CA solute C in diluent phase A
CS solute C in solvent phase S
SS solvent S in solvent phase S
AA diluent A in diluent phase A
AS diluent A in solvent phase S
SA solvent S in diluent phase A.
 Solute C

\ Tieline

locus

20

100
0 Molo/' 0
Diluent A

(a)

0
+
9 .
m

L -1

C I (A + C), A-rich phase

(C)

Figure 14.2. Equilibria in a ternary system, type 11, with two pairs of partially miscible liquids; A = hexane, B =aniline, C =
methylcyclopentane, at 34.5"C [Darwent and Winkler, J . Phys. Chem. 47, 442 (194311. (a) Equilateral triangular plot.
(b) Right triangular plot with tielines and tieline locus. (c) Rectangular coordinate plot with tieline correlation below,
also called Janecke and solvent-free coordinates.

461
 extroctnf\StogeStage

1
fill Stoge

2 3
Fin

Settler m2 . Settler Sett I e r

T.
Feed -

S * Fresh solvent R = Raffinofe

Fa Feed 10 be exlrocfed 0 Exfroc l

(b) (C)

Figure 14.3. Representation of countercurrent extraction batteries. (a) A battery of mixers and settlers (or separators).
(b) Schematic of a three-stage countercurrent battery. (c) Simulation of the performance of a three-stage continuous
countercurrent extraction battery with a series of batch extractions in separatory funnels which are designated by circles on
the sketch. The numbers in the circles are those of the stages. Constant amounts of feed F and solvent S are mixed at
the indicated points. As the number of operations is increased horizontally, the terminal compositions E, and R , approach
asymptotically the values obtained in continuous countercurrent extraction (Treybal, 1963, p . 360).

(a) (b)

Figure 14.4. Less common examples of ternary equilibria and some temperature effects. (a) The system 2,2,4-tri-methylpentane + nitroethane +
perfluorobutylamine at 25C; the Roman numerals designate the number of phases in that region [Vreeland and Dunlap, J. Phys. Chem. 61,
329 (1957)l. (b) Same as (a) but at 51.3"C. (c) Gly-12 different regions exist at 14C [Francis, J. Phys. Chem. 60, 20 (1956)).
+ at 24C;
(d) Docosane furfural + diphenylhexane at several temperatures [Varreressian and Fenrke, Ind. Eng. Chem. 29, 270 (1937) l.(e) Formic acid +
col+dodecanol+nitroethane

benzene + tribromomethane at 70C; the pair formic acid/benzene is partially miscible with 15 and 90% of the former at equilibrium at 2YC, 43
and 80% at 7 0 T , but completely miscible at some higher temperature.
(f) Methylcyclohexane +
water + -picoline at 20"C, exhibiting positive and negative tieline slopes; the horizontal tieline is
called solutropic (Landolt-Bornstein 1126).

462

a1
(e)
Figure 14.4-(continued)
Ishida, Bull. Chern. SOC. Jpn. 33, 693 (1960):
xCSxSA/xCAxSS = K ( X AS X S A/ X AAX S S ) n '
Othmer and Tobias, Ind. Eng. Chern. 34, 693 (1942):
(1 - xSS)/xSS = K[(l - xAA)/xAAln.
Hand, J . Phys. Chern. 34, 1961 (1930):
x C S / x S S= K ( X C A / X A A ) n .
These equations should plot linearly on log-log coordinates; they are
tested in Example 14.1.
A system of plotting both binodal and tieline data in terms of
certain ratios of concentrations was devised by Janecke and is
illustrated in Figure 14.1(c). It is analogous to the enthalpy-
concentration or Merkel diagram that is useful in solving distillation
problems. Straight line combining of mixture compositions is valid in
this mode. Calculations for the transformation of data are made most
conveniently from tabulated tieline data. Those for Figure 14.1 are
made in Example 14.2. The x-y construction shown in
14. 2. CALCULATION OF STAGE
REQUIREMENTS 463
Diphenylhexane
,os
Figure 14.2 is the basis for a McCabe-Thiele construction for finding
the number of extraction stages, as applied in Figure 14.7.
14.2. CALCULATION OF STAGE REQUIREMENTS
Although the most useful extraction process is with countercurrent
flow in a multistage battery, other modes have some application.
Calculations may be performed analytically or graphically. On
flowsketches like those of Example 14.1 and elsewhere, a single box
represents an extraction stage that may be made up of an individual
mixer and separator. The performance of differential contactors such
as packed or spray towers is commonly described as the height
to a stage (HETS) in ft Or m.
'INGLE STAGE
nematerial balance is
feed + solvent = extract + raffinate,
F + S = E + R.
This nomenclature is shown with Example 14.3. On the triangular
diagram, the proportions of feed and solvent locate the mix point
 464 EXTRACTION AND LEACHING

NITROBENZENE

(a)

PROPANE

0.90
OI L

Figure 14.5. Representation of solvent extraction behavior in terms of certain properties rather than direct compositions [Dunstun et LIZ., Sci.
Pet., 1825-1855 (1938)l. (a) Behavior of a naphthenic distillate of VGC = 0.874 with nitrobenzene at 10C. The viscosity-gravity constant is

low for paraffins and high for naphthenes. (b) Behavior of a kerosene with 95% ethanol at 17C. The aniline point is low for aromatics and
naphthenes and high for paraffins. (c) Behavior of a dewaxed crude oil with liquid propane at 70F, with composition expressed in terms of
specific gravity.

M. The extract E and raffinate R are located on opposite ends of the IMMISCIBLE SOLVENTS
tieline that goes through M.
The distribution of a solute between two mutually immiscible solvents
CROSSCURRENT EXTRACTION can be represented by the simple equation,

In this process the feed and subsequently the raffinate are treated in Y=K'X,
successive stages with fresh solvent. The sketch is with Example 14.3.
With a fixed overall amount of solvent the most efficient process is where
with equal solvent flow to each stage. The solution of Example 14.3
shows that crosscurrent two stage operation is superior to one stage X = mass of solute/mass of diluent,
with the same total amount of solvent. Y = mass of solute/mass of solvent.
 14.2. CALCULATION OF STAGE REQUIREMENTS 465

i ne

Figure 14.6. Construction of points on the distribution and operating curves: Line ab is a tieline. The dashed line is the tieline locus.
Point e is on the equilibrium distribution curve, obtained as the intersection of paths be and ade. Line Pfg is a random line from the difference
point P and intersecting the binodal curve in f and g. Point j is on the operating curve, obtained as the intersection of paths gj and f i j .

When K' is not truly constant, some kind of mean value may be
applicable, for instance, a geometric mean, or the performance of
the extraction battery mai be calculated stage by stage with a

different value of K' for each. The material balance around the first
stage where the raffinate leaves and the feed enters and an
intermediate stage k (as in Fig. 14.8, for instance) is

EXAMPLE14.1
The Equations for Tieline Data
The tieline data of the system of Example 14.1 are plotted
according to the groups of variables in the equations of Ishida,

Hand, and Othmer and Tobias with these results:

Ishida:

Hand:
Othmer and Tobias: y = 0 . 8 8 ~ ~[Eq..~(14.4)J.
LOG X . VARIOUS SCALES
 466 EXTRACTION AND LEACHING

EXAMPLE14.2 Calculated ratios for the Janecke coordinate plot of Figure 14.1:
Tabulated Tieliie and Distribution Data for the System A
= 1-Hexene, B = Tetramethylene Sulfone, C = Benzene, Left Phase
Represented in Figure 14.1
Experimental tieline data in mol %: B
A+C
0.0108
0.0135
0.0185
A 0.0248
98.945 0.0346
92.197 0.0513
83.572 0.0721
75.356 0.1038
68.283 0.1790
60.771
54.034 The x-y plot like that of Figure 14.6 may be made with the tieline
47.748 data of columns 5 and 2 expressed as fractions or by projection from
39.225 the triangular diagram as shown.

the material balance becomes solution for the number of stages is

( A / K ) Y F+ X k - l = A X k + X,,.
(14.12
When these balances are made stage-by-stage and intermediate )
compositions are eliminated, assuming constant A throughout, the
result relates the terminal compositions and the number of stages. The When A is the only unknown, it may be found by trial solution of
expression for the fraction extracted is these equations, or the Kremser-Brown stripping chart may be used.
Example 14.4 applies these results.
(14.11)
14.3. COUNTERCURRENT OPERATION

This is of the same form as the Kremser-Brown equation for gas In countercurrent operation of several stages in series, feed enters
abso'rption and stripping and the Turner equation for leaching. The the first stage and final extract leaves it, and fresh solvent enters the
last stage and final raffinate leaves it. Several representations of

C
LinEquilibriue 4' m

xC
I/ lperat ibg

/ A
.ine I

XCR~ xC F XCR,

xc in raffinate

Figure 14.7. Locations of operating points P and Q for feasible, total, and minimum extract reflux on triangular diagrams, and stage
requirements determined on rectangular distribution diagrams. (a) Stages required with feasible extract reflux. (b) Operation at total reflux and
minimum number of stages. (c) Operation at minimum reflux and infinite stages.
 14.3. COUNTERCURRENT OPERATION 467

yi I
I

YY I
I
I

J
XCR~ xC F xC R,
xc in raffinate

X^ -

C' R N C' F xC R,

xc in raffinate

Figure 14.7-(continued)

such processes are in Figure 14.3. A flowsketch of the process

The operation of finding the number of stages consists of a
together with nomenclature is shown with Example 14.5. The overall
material balance is number of steps:

1. Either the solvent feed ratio or the compositions E , and R

F+S=E,+R,
, serve to locate the mix point M.
or 2. The operating point P is located as the intersection of lines FE,
and R,S.
F-E,=R,-S= 3. When starting with E , , the raffinate R , is located at the
other end of the tieline.
The intersection of extended lines FE, and R,S locates the operating 4. The line PR , is drawn to intersect the binodal curve in E,.
point P . The material balance from stage 1 through k is
The process is continued with the succeeding values R,, E,, R, ,
E,, . . . until the final raffinate composition is reached.
F + Ek+l = E , + Rk
When number of stages and only one of the terminal
compositions are fixed, the other terminal composition is selected by
or
trial until the stepwise calculation finds the prescribed number of
stages. Example 14.6 applies this kind of calculation to find the stage
F - E , = Rk - Ektl = P. requirements for systems with Types I and I1 equilibria.
Accordingly, the raffinate from a particular stage and the extract from Evaluation of the numbers of stages also can be made on
a succeeding one are on a line through the operating point P . rectangular distribution diagrams, with a McCabe-Thiele kind of
Raffinate Rk and extract E , streams from the same stage are located construction. Example 14.5 does this. The Janecke coordinate plots
like those of Figures 14.1 and 14.2 also are convenient when many
at opposite ends of the same tieline.
stages are needed, since then the triangular construction may
 468 EXTRACTION AND LEACHING

EXAMPLE14.3 balance are

Single Stage and Cross Current Extraction of Acetic Acid
from Methylisohutyl Ketone with Water
The original mixture contains 35% acetic acid and 65% MIBK. It is
charged at 100 kg/hr and extracted with water. Acetic acid
MlBK
Water
a. In a single stage extractor water is mixed in at 100
kdhr
kg/hr. On the triangular diagram, mix point M is midway
between F and S. Extract and raffinaLe compositions are on the b. The flowsketch of the crosscurrent process is shown. Feed
tieline through M. Results read off the diagram and calculated to the first stage and water to both stages are at 100 kg/hr. The
with material extract and raffinate compositions are on the tielines passing
through mix points M I and M2.Point M is for one stage with the
same total amount of solvent. Two stage results are:

Acetic acid
.- MlBK
Water
0
kdhr
m
.U
m0
C
._
c
e
c
1
5

.u-
0'5
m (Aceticacid)

c
mu
. s-
c

L
e

0 0.5 o1:

Ketone Mass fraction water Water

become crowded and difficult to execute accurately unless a very
large scale is adopted. The Janecke method was developed by
Maloney and Schubert [Trans. AZChE 36, 741 (1940)]. Several
detailed examples of this kind of calculation are worked by Treybal
(1963), Oliver (Diffusional Separation Processes, Wiley, New York,
1966), and Laddha and Degaleesan (1978).
MINIMUM SOLVENT/FEED RATIO
Both maximum and minimum limits exist of the solvent/feed ratio.
The maximum is the value that locates the mix point M on the binodal
curve near the solvent vertex, such as point M,, on Figure 14.7(b).
When an operating line coincides with a tieline, the number of stages
will be infinite and will correspond to the minimum solvent/feed ratio.
The pinch point is determined by the intersection of some tieline with
line R,S. Depending on whether the slopes of the tielines are negative
or positive, the intersection that is closest or farthest from the solvent
vertex locates the operating point for minimum solvent. Figure 14.9
shows the two
cases. Frequently, the tieline through the feed point determines the
minimum solvent quantity, but not for the two cases shown.
EXTRACT REFLUX
Normally, the concentration of solute in the final extract is limited to
the value in equilibrium with the feed, but a countercurrent stream
that is richer than the feed is available for enrichment of the extract.
This is essentially solvent-free extract as reflux. A flowsketch and
nomenclature of such a process are given with Example 14.7. Now
there are two operating points, one for above the feed and one for
below. These points are located by the following procedure:
1. The mix point is located by establishing the solvent/feed ratio.
2. Point Q is at the intersection of lines R,M and E,S,, where
S, refers to the solvent that is removed from the final extract, and
may or may not be of the same composition as the fresh solvent S.
Depending on the shape of the curve, point Q may be inside
 EXTRACT 14.3. COUNTERCURRENT OPERATION
469

the binodal curve as in Example 14.7, or outside as in Figure 14.7.

3. Point P is at the intersection of lines R,M and E,S,, where

S, refers to the solvent removed from the extract and may or may
not be the same composition as the fresh solvent S.

Determination of the stages uses Q as the operating point until

the raffinate composition R, falls below line FQ . Then the operation
is continued with operating point P until R, is reached.

MINIMUM REFLUX
For a given extract composition E,, a pinch point develops when an
operating line through either P or Q coincides with a tieline.
'N- 1' 'i.
Frequently, the tieline that passes through the feed point F determines
the reflux ratio, but not on Figure 14.7(c). The tieline that intersects
FN' 'iN line FS, nearest point S, locates the operating point Q, for minimum
reflux. In Figure 14.7(c), intersection with tieline Fcde is further
away from point S, than that with tieline ubQ,, which is the one that
RAFFINATE
locates the operating point for minimum reflux in this case.

Figure 14.8. Model for liquid-liquid extraction. Subscript i refers to a
component: i = 1,2, . . . , c. In the commonest case, F, is the only
feed stream and FN is the solvent, or F, may be a reflux stream.
Withdrawal streams U, can be provided at any stage; they are not
incorporated in the material balances written here.
MINIMUM STAGES
As the solvent/feed ratio is increased, the mix point M approaches the
solvent point S, and poles P and Q likewise do so. At total reflux all
of the points P, Q, S, S, and M coincide; this is shown in Figure
14.7(b).
Examples of triangular and McCabe-Thiele constructions for
feasible, total, and minimum reflux are shown in Figure 14.7.
 EXAMPLE14.4
Extraction with an Immiscible Solvent
A feed containing 30wt % of propionic acid and 70wt %
trichlorethylene is to be extracted with water. Equilibrium distribution
of the acid between water (Y) and TCE ( X ) is represented by Y =
K'X, with K' = 0.38. Section 14.3 is used.

a. The ratio EIR of water to TCE needed to recover 95% of

the acid in four countercurrent stages will be found:

X , = 30/70,
X,,= 1.5170,
Ys= 0,
@ = (30 - 1.5)/(30 - 0) = 0.95 = (A5- A / ( A 5 - 1).

By trial,

A = 1.734,
EIR =A/K' = 1.73410.38= 4.563.

b. The number of stages needed to recover 95% of the acid with

EIR = 3.5 is found with Eq. 14.12.

A = K'EIR = 0.38(3.5) = 1.330, @ = 0.95,

n = - l + ln[(A - @M1- $11 = -1

In A
+ ln[(1.330 - 0.95)/(1 - 0.95)]/1n(1.330) = 6.11
470 EXTRACTION AND LEACHING tieline with horizontals from the left-hand end of the tielines and
reflected from the 45 line.

The operating curve is drawn similarly with horizontal

EXAMPLE14.5
Countercurrent Extraction Represented on Triangular
and Rectangular Distribution Diagrams
The specified feed F and the desired extract E , and raffinate R ,
compositions are shown. The solvent/feed ratio is in the ratio of the
line segments MSIMF, where the location of point M is shown as the
intersection of lines E,RN and FS.
Phase equilibrium is represented by the tieline locus. The
equilibrium distribution curve is constructed as the locus of
intersections of horizontal lines drawn from the right-hand end of a
projections from pairs of random points of intersection of the binodal
curve by lines drawn through the difference point P. Construction of
these curves also is explained with Figure 14.6.
The rectangular construction shows that slightly less than eight
stages are needed and the triangular that slightly more than eight are
needed. A larger scale and greater care in construction could bring
these results closer together.
 Rk-1
Naturally, the latter constructions are analogous to those for
distillation since their forms of equilibrium and material balances are
the same. References to the literature where similar calculations are
performed with Janecke coordinates were given earlier in this section.
Use of reflux is most effective with Type I1 systems since then
essentially pure products on a solvent-free basis can be made. In
contrast to distillation, however, extraction with reflux rarely is
beneficial, and few if any practical examples are known. A related
kind of process employs a second solvent to wash the extract
countercurrently. The requirements for this solvent are that it be only
slighly soluble in the extract and easily removable from the extract
and raffinate. The sulfolane process is of this type; it is described, for
example, by Treybal (1980) and in more detail by Lo et al. (1983, pp.
541-545).
EXAMPLE14.6
Stage Requirements for the Separation of a Type I and a
Type I1 System
a. The system with A = heptane, B = tetramethylene
sulfone, and C = toluene at 50C [Triparthi, Ram, and
Bhimeshwara, J . Chem. Eng. Data 20,261 (1975)l: The feed
contains 40% C, the extract 70% C on a TMS-free basis or
60% overall, and raffinate 5% C. The construction shows that
slightly more than two equilibrium stages are needed for this
separation. The compositions of the streams are read off the
diagram:
Feed Extract Raffinate
Heptane 60 27 2
TMS 0 13 93
Toluene 40 60 5 2,2,4-trimethylpentane at 25C [Hwa, Techo, and Ziegler, J .
-F
Q)X
. c-
E
14.4. LEACHING OF SOLIDS
Leaching is the removal of solutes from admixture with a solid by
contracting it with a solvent. The solution phase sometimes is called
the overflow, but here it will be called extract. The term underflow or
raffinate is applied to the solid phase plus its entrained or occluded
solution.
Equilibrium relations in leaching usually are simpler than in
liquid-liquid equilibria, or perhaps only appear so because few
measurements have been published. The solution phase normally
contains no entrained solids so its composition appears on the
hypotenuse of a triangular diagram like that of Example 14.8. Data
for the raffinate phase may be measured as the holdup of solution by
the solid, K Ib solution/lb dry (oil-free) solid, as a function of the
concentration of the solution, y Ib oil/lb solution. The correspond-
14.4. LEACHING OF SOLIDS 471
The material balance on heptane is
40 = 0.6E + 0.05(100 - E),
whence E = 63.6 lb/100 lb feed, and the TMS/feed ratio is
0.13(63.6) + 0.93(36.4) = 42 lb/100 Ib feed.
b. The type I1 system with A=octane, B =nitroethane, and C =
Chem. Eng. Datu 8, 409 (1963)l: The feed contains 40% TMP,
the extract 60% TMP, and the raffinate 5% TMP. Again, slightly
more than two stages are adequate.

C E.

ing weight fraction of

x = K y / ( K + 1).

Since the raffinate is a mixture of the solution and dry solid, the
equilibrium value in the raffinate is on the line connecting the origin
L
C

A
B

Figure 14.9. Minimum solvent amount and maximum extract concentration. Determined by location of the intersection of extended tielines with
extended line R,S. (a) When the tielines slope down to the left, the furthest intersection is the correct one. (b) When the tielines slope down to the
right, the nearest intersection is the correct one. At maximum solvent amount, the mix point M,,,is on the binodal curve.
 472 EXTRACTION AND LEACHING

EXAMPLE14.7 made with operating point P, which is the intersection of lines FQ

Countercurrent Extraction Employing Extract Reflux and SRN.
The feed F, extract E , , and raffinate R N are located on the triangular In this example, only one stage is needed above the feed F
diagram. The ratio of solvent/feed is specified by the location of the and five to six stages below the feed. The ratio of solvent to feed is
point M on line SF.
Other nomenclature is identified on the flowsketch. The solvent- S / F = FM/M S = 0.196,
free reflux point R , is located on the extension of line S E I .
Operating point Q is located at the intersection of lines SR, and and the external reflux ratio is
RNM . Lines through Q intersect the binodal curve in compositions
of raffinate and reflux related by material balance: for instance, R,
and E,+, . When the line Q F is crossed, further constructions are r = E,,/E,, = (R,S/R,E,)(QE,/SQ) = 1.32.

Solvent

L
I Removal
Solvent
Reflux
'Pgdduct

RN -F R,SSolvent

Flowsketch and triangular diagram construction with extract reflux.

EXAMPLE14.8 and some calculated values are

Leaching of an Oil-Bearing Solid in a Countercurrent Battery
Oil is to be leached from granulated halibut livers with pure ether as y 0 0.1 0.2 0.3 0.4 0.5 0.6 0.7 0.8
solvent. Content of oil in the feed is 0.32Ib/Ib dry (oil-free) solids x 0 0.0174 0.0397 0.0694 0.1080 0.1565 0.2147 0.2821
and 95% is to be recovered. The economic upper limit to extract 0.3578
concentration is 70% oil. Ravenscroft [Znd. Eng. Chem. 28, 851
Points on the raffinate line of the triangular diagram are located on
(1934)l measured the relation between the concentration of oil in the
lines connecting values of y on the hypotenuse (solids-free) with the
solution, y , and the entrainment or occlusion of solution by the solid
origin, at the values of x and corresponding y from the preceding
phase, K Ib solution/lb dry solid, which is represented by the equation
tabulation.

Feed composition is xF = 0.3211.32 = 0.2424.

K = 0.19 + 0 . 126~+ 0.810y2. Oil content of extract is y, = 0.7.
Oil content of solvent is y , = 0.
The oil content in the entrained solution then is given by Amount of oil in the raffinate is 0.32(0.05) = 0.016 Ib/lb dry, and
the corresponding entrainment ratio is
x=K/(K + l)y, wt fraction,
KN = 0.016/yN = 0.19 + 0 . 1 2 6 ~+~0 . 81~5 .
 14.5. NUMERICAL CALCULATION OF MULTICOMPONENT EXTRACTION
EXAMPLE 14.&(continued)
Solving by trial,
yN = 0.0781,
KN = 0.2049,
xN = 0.0133 (final raffinate composition).
The operating point P is at the intersection of lines FE, and SR,. The
triangular diagram construction shows that six stages are needed.
The equilibrium line of the rectangular diagram is constructed
with the preceding tabulation. Points on the material balance line
lines FE, and SR,. Similarly, equilibrium compositions R, and E, are
on a line through the origin. Example 14.8 evaluates stage
requirements with both triangular diagram and McCabe-Thiele
constructions. The mode of construction of the McCabe-Thiele
diagram is described there.
These calculations are of equilibrium stages. The assumption is
made that the oil retained by the solids appears only as entrained
solution of the same composition as the bulk of the liquid phase. In
some cases the solute may be adsorbed or retained within the
interstices of the solid as solution of different concentrations. Such
deviations from the kind of equilibrium assumed will result in stage
efficiencies less than 100% and must be found experimentally.
473
are located as intersections of random lines through P with these
results:
Y O 0.1 0.2 0.3 0.4 0.5 0.6 0.7
x 0.013 0.043 0.079 0.120 0.171 0.229 0.295 0.368
The McCabe-Thiele construction also shows that six stages are
needed.
Point P is at the intersection of lines E,F and SR,. Equilibrium
compositions are related on lines through the origin, point A.
Material balance compositions are related on lines through the
operating point P.
14.5. NUMERICAL CALCULATION OF
MULTICOMPONENT EXTRACTION
Extraction calculations involving more than three components cannot
be done graphically but must be done by numerical solution of
equations representing the phase equilibria and material balances over
all the stages. Since extraction processes usually are adiabatic and
nearly isothermal, enthalpy balances need not be made. The solution
of the resulting set of equations and of the prior determination of the
parameters of activity coefficient correlations requires computer
implementation. Once such programs have been developed, they also
may be advantageous for ternary extractions,
 474
particularly when the number of stages is large or several cases must
be worked out. Ternary graphical calculations also could be done on a
computer screen with a little effort and some available software.
The notation to be used in making material balances is shown on
Figure 14.8. For generality, a feed stream Fk is shown at every stage,
and a withdrawal stream u k also could be shown but is not
incorporated in the balances written here. The first of the double
subscripts identifies the component i and the second the stage
number k ; a single subscript refers to a stage.
For each component, the condition of equilibrium is that its
activity is the same in every phase in contact. In terms of activity
coefficients and concentrations, this condition on stage k is written:
Y%ik
EXTRACTION AND LEACHING When all of the coefficients are known, this can be solved for the
concentrations of component i in every stage. A straightforward
method for solving a tridiagonal matrix is known as the Thomas
algorithm to which references are made in Sec. 13.10, Basis for
Computer Evaluation of Multicomponent Separations: Specifi-
cations.
INITIAL ESTIMATES
Solution of the equations is a process in which the coefficients of Eq.
(14.28) are iteratively improved. To start, estimates must be made of
the flow rates of all components in every stage. One procedure is to
assume complete removal of a light key into the extract and of the
heavy key into the raffinate, and to keep the solvent in the extract
phase throughout the system. The distribution of the keys in the
intermediate stages is assumed to vary linearly, and they must be
= y$zk made consistent with the overall balance, Eq. (14.27), for each
component. With these estimated flowrates, the values of xik and yik
are evaluated and may be used to find the activity coefficients and
(14.19) distribution ratios, K i k . This procedure is used in Example 14.9.

where
PROCEDURE
Kik = %/r,,
The iterative calculation procedure is outlined in Figure 14.10. The
is the distribution ratio. The activity coefficients are functions of the method is an adaptation to extraction by Tsuboka and Katayama
temperature and the composition of their respective phases: (1976) of the distillation calculation procedure of Wang and Henke
[Hydrocurb. Proc. 45(8), 155-163 (1967)]. It is also presented by
(14.21) Henley and Seader (1981, pp. 586-594).
(14.22)
1. The initial values of the flowrates and compositions xik and yik are
The most useful relations of this type are the NRTL and UNIQUAC estimated as explained earlier.
which are shown in Table 14.1. 2. The values of activity coefficients and distribution ratios
Around the kth stage, the material balance is are evaluated.
3. The coefficients in the tridiagonal matrix are evaluated
from Eqs. (14.24)-(14.26). The matrix is solved once for each
component.
When combined with Eq. (14.19), the material balance becomes
4. The computed values of iteration ( r + 1) are compared
with those of the preceding iteration as
Rk-lXi,k-l - (Rk + EkKik)xik + Ek+lKi,k+lXi,k+l = -Fkzik.

z1 E
In the top stage, k = 1 and R, = 0 so that
i=l

-(Rl + VIK,&il + E , K i g i 2 = -FIzil.

The magnitude, O.OlNC, of the convergence criterion is
arbitrary.
In the bottom stage, k = N and E N + ]= 0 so that
5. For succeeding evaluations of activity coefficients, the
R N - l x z , N - I- ( R N + E N K L X t N = -FNz,N. values of the mol fractions are normalized as
The overall balance from stage 1 through stage k is

(14.30)

which is used to find raffinate flows when values of the extract flows have
l2 beenestimated. 6. When the values of xik have converged, a new set of yik is
For a ll stages for a component i, Eqs. (14.24)-(14.26) constitut e a tridiagonal matrix which is writt en
]]
calculated with
Bl Cl y rk = K .I G .rk
BNC, - l cN-I ][: xrN-l = DN[- l (14.28)

-
.I . A new set of extract flow rates is calculated from
C
E t + ) = E f) 2 yikt
i=1
AN BN xzN DN where s is the outer loop index number.
 475
14.5. NUMERICAL CALCULATION OF MULTICOMPONENT EXTRACTION

TABLE 14.1. NRTL and UNIQUAC Correlations for Activity Coefficients of

Three-Component Mixturesa

X2Gi2
-I

Gl2xl -k x2

r..= 0

G;;= 1

UNIQUAC
6;
In yi = In- + 5qi In-
ei
+ 1; - -@i(x1Il + +
x212 x313) + qi[ 1 - ln(Olrli + 02r2 + 83qi)]

xi 9; xi

'NRTL equation: There is a pair of parameters gik and gkj for each pair of substances in the
mixture; for three substances, there are three pairs. The other terms of the equations are related
to the basic ones by

Tjk = gjk/RT,
GI*. = exp(-aikrik).

For liquid-liquid systems usually, a;., 3 0.4.

UNIQUAC equation: There is a pair of parameters uik and uki for each pair of substances in
the mixture:

tik= exp(-uik/RT).

The terms with single subscripts are properties of the pure materials which are usually known or
can be estimated.
The equations are extended readily to more components.
(See, for example, Walas, Phase Equilibria in Chemical Engineering, Butterworths, 1985).

8. The criterion for convergence is

N

Tz= (1 - ~ j s ) / ~ j s + 5l) E* ) ~= 0 . 0 1 ~ .
k=l

The magnitude, 0.01N, o f the convergence

arbitrary.
 476 EXTRACTION AND LEACHING

EXAMPLE14.9 TABLE 2. Estimated Mol Fractions

Trial Estimates and Converged Flow Rates and
Compositions in All Stages of an Extraction Battery for a
Four-Component Mixture
Benzene is to be recovered from a mixture with hexane using
aqueous dimethylformamide as solvent in a five-stage extraction 1 0.0 0.0909 0.6818 0.2273 0.7895 0.2105 0.0
battery. Trial estimates of flow rates for starting a numerical solution 0.0
are made by first assuming that all of the benzene and all of the 2 0.0 0.0741 0.6944 0.2315 0.8333 0.1667 0.0
solvent ultimately appear in the extract and all of the hexane appears 0.0
in the raffinate. Then flow rates throughout the battery are assumed 30.0 0.0566 0.7076 0.2359 0.8824 0.1176 0.0 0.0
to vary linearly with stage number. Table 1 shows these estimated 40.0 0.0385 0.7211 0.2404 0.9375 0.0625 0.0 0.0
flowrates and Table 2 shows the corresponding mol fractions. Tables 5 0.0 0.0196 0.7353 0.2451 1.0000 0.00.0 0.0
3 and 4 shows the converged solution made by Henley and Seader
(1981, p. 592); they do not give any details of the solution but the TABLE 3. Converged Mol Fractions
algorithm of Figure 14.10 was followed.

Stage
j

1 0.0263 0.0866 0.6626 0.2245 0.7586 0.1628 0.0777

TABLE 1. Estimated mol/hr 0.0009
2 0.0238 0.0545 0.6952 0.2265 0.8326 0.1035 0.0633
Extract Raffhate
0.0006
Stage Total H 6 D W Total H 6 D W 3 0.0213 0.0309 0.7131 0.2347 0.8858 0.0606 0.0532
0.0004
1 - 4 0.0198 0.0157 0.7246 0.2399 0.9211 0.0315 0.0471
2 1100 0100750 250 400 300 100 00 0.0003
3 1080 080750 250 380 30080 00 5 0.0190 0.0062 0.7316 0.2432 0.9438 0.0125 0.0434
4 1060 060750 250 360 30060 00 0.0003
5 1040 040750 250 340 3004000
6 1020 020750 250 320 30020 00 TABLE 4. Converged mol/hr
N+1 1000 0 0 750 250 300 300 0 0 0
Extract Raffinate

Hexane 29.3 270.7

Benzene 96.4 3.6
Solutions of four cases of three- and four-component systems DMF 737.5 12.5
Water 249.0 0.1
are presented by Tsuboka and Katayama (1976); the number of outer
loop iterations ranged from 7 to 41. The four component case worked
- -
Total 1113.1 286.9
out by Henley and Seader (1981) is summarized in Example 14.9;
they solved two cases with different water contents of the solvent,
dimethylformamide.

14.6. EQUIPMENT FOR EXTRACTION
Equipment for extraction and leaching must be capable of providing
intimate contact between two phases so as to effect transfer of solute
between them and also of ultimately effecting a complete separation
of the phases. For so general an operation, naturally a substantial
variety of equipment has been devised. A very general classification
of equipment, their main characteristics and industrial applications is
in Table 14.2. A detailed table of comparisons and ratings of 20 kinds
of equipment on 14 characteristics has been prepared by Pratt and
Hanson (in Lo et al., 1983, p. 476). Some comparisons of required
sues and costs are in Table 14.3.
Selected examples of the main categories of extractors are
represented in Figures 14.11-14.15. Their capacities and perfor-
mance will be described in general terms insofar as possible, but
sizing of liquid-liquid extraction equipment always requires some
pilot plant data or acquaintance with analogous cases. Little detailed
information about such analogous situations appears in the open
literature. Engineers familiar with particular kinds of equipment, such
as their manufacturers, usually can predict performance with a
minimum amount of pilot plant data.
Literature data is almost entirely for small equipment whose
capacity and efficiency cannot be scaled up to commercial sizes,
although it is of qualitative value. Extraction processes are sensitive
because they operate with small density differences that are sensitive
to temperature and the amount of solute transfer. They also are
affected by interfacial tensions, the large changes in phase flow rates
that commonly occur, and even by the direction of mass transfer. For
comparison, none of these factors is of major significance in vapor-
liquid contacting.
CHOICE OF DISPERSE PHASE
Customarily the phase with the highest volumetric rate is dispersed
since a larger interfacial area results in this way with a given droplet
sue. In equipment that is subject to backmixing, such as spray and
packed towers but not sieve tray towers, the disperse phase is made
the one with the smaller volumetric rate. When a substantial
difference in resistances of extract and raffinate films to mass transfer
exists, the high phase resistance should be compensated for with
increased surface by dispersion. From this point of view, Laddha and
Degaleesan (1978, pp. 194) point out that water should be the
dispersed phase in the system water + diethylamine + toluene. The
dispersed phase should be the one that wets the material of
construction less well. Since the holdup of continuous phase usually
is greater, the phase that is less hazardous or less expensive should be
continuous. It is best usually to disperse a highly viscous phase.