Extraction Method

Lecture Notes 11 - Solid-Liquid Extraction 1
Engr. Caesar P. Llapitan
I. INTRODUCTION
Leaching is the preferential solution of one or more compounds from a solid mixture by contact with
a liquid solvent. The solvent partially dissolves the solid material so that the desired solute can be
carried away.
Typical users include:

 the metals industry for removing mineral from ores (acid solvents)
 the sugar industry for removing sugar from beets (water is solvent)
 the oilseeds industry for removing oil from soybeans, etc. (hexane or similar organic solvents)
The basic concepts of leaching also apply in the environment, where materials can be leached out
by rainwater and carried into the groundwater supply. A simple, everyday example of a leaching
process is making your morning coffee.
Generally, the process can be considered in three parts: first the change of phase of the solute as it
dissolves in the solvent, secondly its diffusion through the solvent in the pores of the solid to the outside
of the particle, and thirdly the transfer of the solute from the solution in contact with the particles to the
main bulk of the solution. Any one of these three processes may be responsible for limiting the
extraction rate, though the first process usually occurs so rapidly that it has a negligible effect on the
overall rate.
Figure 1 Schematic diagram of leaching process – before extraction (left) and after extraction
(right): (1) solvent (2) extraction material (solid carrier phase with transition component (3) transition
component (4) depleted solid carrier phase (5) solvent with dissolved transition component
Retrieved from Ref [9].
To achieve the fastest and most complete solid extraction possible, the solvent must be provided with
large exchange surfaces and short diffusion paths. This can be done by pulverizing the solid to be
extracted. However, an excessively small grain size can cause agglutination and make it more difficult
for the solvent to permeate.
In the simplest form of this unit operation, the extraction material and the solvent are mixed well. The
solvent and the dissolved transition component are then removed and regenerated.
The extraction material can also take the form of a fixed bed with the solvent flowing through it. In a
further form of the application, the extraction material is led through the solvent.
The solvent is normally regenerated using evaporation/distillation. The solvent is evaporated, and a
concentrated extract solution is left behind as the product. The solvent is condensed and can then
be reused.
II. FACTORS INFLUENCING THE RATE OF EXTRACTION
There are four important factors to be considered:

1. Particle size
The smaller the size, the greater is the interfacial area between the solid and liquid, and therefore
the higher is the rate of transfer of material and the smaller is the distance the solute must diffuse
within the solid as already indicated. On the other hand, the surface may not be so effectively
used with a very fine material if circulation of the liquid is impeded, and separation of the particles
from the liquid and drainage of the solid residue are made more difficult. It is generally desirable
that the range of particle size should be small so that each particle requires approximately the
same time for extraction and, in particular, the production of a large amount of fine material
should be avoided as this may wedge in the interstices of the larger particles and impede the flow
of the solvent.
2. Solvent
The liquid chosen should be a good selective solvent and its viscosity should be sufficiently low for
it to circulate freely. Generally, a relatively pure solvent will be used initially, although as the
extraction proceeds the concentration of solute will increase and the rate of extraction will
progressively decrease, first because the concentration gradient will be reduced, and secondly
because the solution will generally become more viscous.
3. Temperature
In most cases, the solubility of the material which is being extracted will increase with temperature
to give a higher rate of extraction. Further, the diffusion coefficient will be expected to increase
with rise in temperature and this will also improve the rate of extraction. In some cases, the upper
limit of temperature is determined by secondary considerations, such as, for example, the
necessity to avoid enzyme action during the extraction of sugar.
4. Agitation of the fluid

Agitation of the solvent is important because this increases the eddy diffusion and therefore the
transfer of material from the surface of the particles to the bulk of the solution, as discussed in the
following section. Further, agitation of suspensions of fine particles prevents sedimentation and
more effective use is made of the interfacial surface.
III. LIQUID-SOLID EQUILIBRIUM
Liquid-solid phase equilibrium is important in understanding leaching, crystallization, and adsorption.

Diffusion through solids is slow, even though pores in the substance, and so equilibrium is harder to
achieve.
Separation of a solid phase from a liquid phase is done by sedimentation, filtration, or centrifugation.
Complete separation is essentially impossible, so must deal with some degree of liquid entrainment on
any "wet" solid phase.
Principles
Leaching can be batch, semi-batch, or continuous. It usually operates at an elevated temperature
to increase the solubility of the solute in the solvent. Calculations involve three components (solid,
solvent, solute) systems.
Feed to a leaching system typically is solid, consisting of basically insoluble carrier material and a
(usually desirable) soluble compound. The feed usually must be prepared by grinding or chopping. It
is then mixed with a liquid solvent. The desired material dissolves (to some extent) and so leaves when
the liquid is drawn off as overflow. The solids are then removed as underflow. The underflow is wet,
and so some of the solvent/solute mixture is carried out here as well.
Flow through a leaching system may be crosscurrent or countercurrent.
Modeling Assumptions
Modeling a leaching system requires several assumptions to make the system "ideal".
The solubility of solute may have an upper bound, limiting how much solute the solvent may hold.
Ideally, the carrier will not dissolve, and so will not be present in the overflow. This is a generally safe
assumption, although allowance should be made for entrainment of solid flakes, etc., in the overflow
from the first stage.
Mixing of the solid and the solvent is critical. Typically, "perfect mixing" is assumed, as is the idea of an
equilibrium stage (the solid and liquid phases on each stage are in equilibrium). These assumptions
imply that all the liquid within the stage has the same composition and so the overflow and the liquid
carried in the underflow are identical. This is known as the uniform solution assumption and will result
in a linear equilibrium curve.
One also needs to determine how much liquid leaves entrained with the solids in the underflow. The
simplest option is the assumption of constant solution underflow which means that every stage has the
same, fixed ratio of solution to solid in the underflow stream. Like the equimolar overflow assumption
in distillation, this will produce a linear operating curve. The first stage is again problematic, since it
must "wet" the solid (fill pores, etc.) and so will typically pick up more liquid than subsequent stages.
More generally, the amount of solution in the underflow depends on the properties of the solution,
which are dependent on its composition. The amount of solute present seems to affect the "stickiness"
of the solution. As a result, "draining data" is typically collected. This relates the solution/solid ratio to
the composition of the solution and is used to determine the nature of the operating curve.
Operating Equations
As has become customary in this course, we develop the operating equations from the balances
describing the system. The steady state material balance over any stage in a countercurrent flow
system is written as:
0  Vn1  Va  La  Ln (1)
Following McCabe et al. (1993), V is used for the liquid solvent phase and L for the entrained liquid
phase. The subscripts indicate the stage in which the stream originates, with a used for the fresh feed
and b for the final product. Similarly, the component balance is:
0  Vn1yn1  Vaya  Lax a  Lnx n (2)
The operating equation is obtained by rearranging the component balance:
Vn1yn1  Vaya  Lax a  Lnxn (3)
Ln x n Vay a  L a x a
yn1   (4)
Vn1 Vn1
which can be shown to run through the points (xa, ya) and (xb, yb).
In some circumstances, it may be useful to use the total material balance to eliminate V n+1 from the
equation:
Ln x n Vay a  L a x a
yn1  
Va  Ln  L a Va  Ln  L a
1 V y L x (6)
yn1  xn  a a a a
V L Ln  L a  Va
1 a a
Ln
In the general operating case, the density and viscosity of the solution change with the solute
concentration and the mass retained by the solid phase changes from tank to tank. Consequently,
the ratio of entrained liquid to solution varies from stage to stage. In this case, the operating curve is
not linear.
In the special case of constant solution underflow, the mass retained by the solid does not depend on
the concentration and the operating line is linear after the first stage.
IV. CALCULATIONS
Two main types of calculations are usually performed:

1. The extent of leaching is determined, usually by balance calculations. Efficiency depends on
contact time and the liquid-solid separation efficacy. The limit on extent is imposed by
equilibrium constraints.
2. The number of stages required to reduce the solute content to a specified value is determined.
As with distillation, the relationship between the equilibrium and operating lines will be used to
determine the number of stages.
Solution techniques are: 1) stage-to-stage algebraic calculations using the material balance and
equilibrium relations; or 2) graphical methods such as the use of the right triangular, Ponchon-Savarit
or McCabe-Thiele diagram. Graphical solutions may be set up using the actual compositions or on a
"solid-free" basis.
Leaching calculations are almost always based on the principle that the solid will not dissolve into the
solvent. Thus, the concentrations of x solute in the solvent entrained in the slurry and y of the solute in
the solvent liquid phase can be expressed on a solid free basis without significantly changing the
calculation. The equilibrium behavior of the system establishes key behaviors.
Begin with the assumptions that each stage has enough contact time that the system can reach
equilibrium, that there is enough solvent present in each stage to allow equilibrium removal of solute
from solvent, and that the solute will not absorb on the solvent. The uniform solution assumption then
applies, and the equilibrium xy-curve will be a straight line, xe = ye.
Two subsets of the uniform solution case should be noted. In the first, the solute is infinitely soluble in
the solvent. In this case, all values of x and y from 0.0 to 1.0 may be obtained. In the second case, the
solubility is limited to some maximum value, xs. The xy-diagram will be a straight line, but will not go all
the way from 0 to 1. Instead, at xs it will become vertical.
If the conditions (contact time, adequate solvent mass, no adsorption) that determine uniform solution
do not hold, the xy-diagram may be curved (often, it will look like that used in distillation).
Constant Solution Underflow

In the case of constant solution underflow, both the equilibrium and operating curves are linear and
it is possible to solve for the number of stages directly. The general solution is developed using the
Kremser Equation is:
yb  ybe
ln
y a  y ae
N (7)
yb  y a
ln
ybe  y ae
For leaching, the equilibrium line is xe = ye, so the equation becomes:
yb  x b
ln
ya  x a
N (8)
yb  y a
ln
xb  x a
To use this, you need to make sure that La = Ln (that the flow of liquid entrained with the solid is the
same entering and leaving the first stage -- constant solution underflow is specified starting with the
first stage) or calculate the first stage separately.
Variable Solution Underflow

If solution underflow is not constant, the operating equation for leaching is not linear. In this case, an
approach similar to the McCabe-Thiele method for distillation columns can be used.
1. Use system component balances to determine xa and xb.
2. Construct operating curve. In general, the operating curve will not intersect the equilibrium
curve as it did for distillation.
o Select an xn somewhere in the middle. This gives an equivalent Ln.
o Use Ln and a material balance to obtain Vn+1.
o Find yn+1 by a component balance
o Plot (xn, yn+1) as a point on the operating curve.
o Repeat as needed to obtain the full operating curve. Often a single point is adequate.
3. Operating stages may then be stepped off as triangles between the operating and equilibrium
curves in the same fashion as was used for distillation. Normally, you start with the dilute product
composition.
Solid-Free Calculations
Another approach to solving these problems uses a graphical method similar to the Ponchon-Savarit
method for distillation columns; however, a composition-composition diagram is used for construction
rather than an enthalpy-composition diagram. The method assumes that all streams are a mix of solid
and solution and that the ratio of solid to solution can be calculated.
The working plot is constructed using modified compositions. Define a to be the mass (or
concentration) of solute, b the mass of solid (zero for an insoluble carrier), and s the mass of solvent,
then calculate:
a
X  Mass solute/mass solution, and
as
b
Y  Mass insoluble/mass solution
as
and plot Y vs. X. Since there are two phases (overflow and underflow), there will be two curves.
The upper curve will be a line if solution underflow is constant. The lower curve will collapse to the X
axis (Y = 0) when the carrier is completely insoluble. The curves are connected by tie-lines, based on
the relationship between the phases. If the uniform solution condition holds so that xe = ye, these will
be vertical; if not, they will be slanted and must be determined. Generally speaking, the equilibrium
data must be obtained experimentally.
Once the composition diagram is constructed, a "J point" may be determined. This is useful in some,
but not all problems. J is defined as the in terms of the total amount of solute entering (or leaving,
they're equal at steady state):
J = Vb + La Or J = Va + Lb
Graphically, J is the intersection of the line connecting Va with Lb and that connecting Vb and La. The
J point is not used in the actual construction of stages; it can be used for lever arm calculations.
The "P point" is used in the constructions. It is given by the equations:
P = Va – La Or P = Vb – Lb
P represents the "net flow" of material through the system, so that
Vn1  Ln  P (9)
Effectively, this point pretends that there are mixers on either end of the leaching process, combining
both the L and V flows into a single stream. This is thus a fictitious value, and one coordinate must be
negative.
Operating lines are constructed by connecting an L point with the P point. The intersection with the
axis will be the V point for the next stage.
Begin construction at Va point. First trace upward to the equilibrium curve along a tie line (remember,
the tie lines are vertical when the uniform solution conditions hold). This will be the L1 point. Next
construct a line by connecting L1 to P. The V2 point will lie at the intersection of this line and the X-axis
(the operating curve). Trace up a tie line to L2, construct a line to find V3, etc. Continue to alternate
between the tie lines and constructed operating lines until the Vb point has been passed. The number
of triangles formed will correspond to the number of leaching stages required.
V. EXAMPLES SOLID-LIQUID EXTRACTION
A. Rectangular Triangle Diagram Method
Nomenclature:
C= inert material
A = extractable material
S = solvent
a = constant underflow
b = variable underflow
c = constant ratio solvent/inert material
DE = connode
x = composition of underflow
y = composition of overflow
Horizontal line = locus of the composition of the mixture containing inert and solute
(A and C)
Vertical line = locus of the composition of the mixture containing inert and solvent
(C and S)
Hypotenuse = locus of the composition of the mixture containing solute and solvent
(A and S)
S
1
Overflow (Extract)
c
E
b
a
0 1
C A
Figure 2 Rectangular Triangle Diagram
Material Balance
V, yV OVERFLOW
F, xF
FEED L, xL UNDERFLOW
Figure 3 Control volume for material balance in leaching process
Overall Material Balance F = V +L (10)
Component Balance FxF = Vy V + Lx L (11)
Vy V  Lx L
xF  (12)
V L
V  yC V  L  x C L
Inert solid balance  x C F  (13)
V L
V  y A V  L  x A L
Solute balance  x A F  (14)
V L
V  yB V  L  x B L
Solvent balance  xB F  (15)
V L
If (xA or yA) versus (xS or yS) is plotted, the points L, V and F lie on a straight line.
Locus of the Overflow

This represents the locus of the composition of the underflow and depends upon the amount of
solution retained per unit amount of inert solids.
Case 1:
S
weight of solution retained
 constant  k
weight of inert solid
Equation of a straight line: xS or yS

k
xS   xA
k 1
k C A
If xA = 0: xS 
k 1 xA or yA
Figure 4 Case 1 right triangular diagram
k
If xS = 0: xA 
k 1
Thus, the locus of the underflow is parallel to the hypotenuse
Case 2:
S
weight of solvent retained
 constant  k
Equation of a straight line:

xS or yS
k
xS  1 x A 
k 1
k
If xA = 0: xS  C A
k 1 xA or yA
If xS = 0: xA  1 Figure 5 Case 2 right triangular diagram
Case 3: S
weight of solution retained
 f(composition)
xS or yS
C A
xA or yA
Determining the Number of Stages Figure 6 Case 3 right triangular diagram
V1, y1 Vn+1, yn+1

1 2 n–1 n
L0 , x 0 Ln , x n
Figure 7 Multi-stages leaching process
Overall material balance: L0 + Vn+1 = V1 + Ln (16)
Component balance: L0 x 0 + Vn+1 yn+1 = V1 y1 + Ln xn (17)
Let J = addition point: J = L0 + Vn+1 = V1 + Ln (18)

xJ = composition of J
Then
L0 x 0 + Vn+1 yn+1 = Jx j  V1 y1 + Ln xn (19)
Therefore, (x0, yn+1, xj) and (xn, y1, xj) lie on a straight intersecting at point J
If we let P = difference point
P = V1  L0 = Vn+1  Ln (20)
Hence, (y1, x0, xp) and (yn+1, xn, xp) lie on a straight-line intersecting at point P
Procedure in determining the number of stages:

1. Locate the underflow and the overflow locus on yn+1
the triangular diagram and past the point x0, xn,
y1 and yn+1.
2. Connect x0 with yn+1 and xn with y1; the
intersection being xj
3. Connect x0 with y1 and xn with yn+1 intersecting at
point P y3
4. Find the number of ideal stages: y2
a. Connect y1 with the right angle vertex of y1
the triangle intersecting the underflow x1
locus at x . This is an equilibrium tie line
(x1, y1)
b. Connect x1 with P, intersecting the xn x0
overflow locus at y2.
c. Connect y2 with the right angle vertex
intersecting the underflow at x2.
d. Repeat the procedure until xn is reached. P
5. Count the number of tie lines. Number of tie lines Figure 8 Right triangular diagram for
is the number of ideal stages. determination of number of stages
Exercises 1: Retrieved from Ref [5]

1. Seeds, containing 20 per cent by mass of oil, are extracted in a countercurrent plant, and 90
per cent of the oil is recovered in a solution containing 50 per cent by mass of oil. If the seeds
are extracted with fresh solvent and 1 kg of solution is removed in the underflow in association
with every 2 kg of insoluble matter, how many ideal stages are required?
2. Halibut oil is extracted from granulated halibut livers in countercurrent multi-batch
arrangement using ether as the solvent. The solids charge contains 0.35 kg oil/kg exhausted
livers and it is desired to obtain a 90 per cent oil recovery. How many theoretical stages are
required if 50 kg ether is used/ 100 kg untreated solids? The entrainment data are:
Concentration of overflow
0 0.1 0.20 0.30 0.40 0.50 0.60 0.67
(kg oil/kg solution)
Entrainment
(kg solution retained/kg 0.28 0.34 0.40 0.47 0.55 0.66 0.80 0.96
extracted livers)
3. Seeds containing 25 per cent by mass of oil are extracted in a countercurrent plant and 90
per cent of the oil is to be recovered in a solution containing 50 per cent of oil. It has been
found that the amount of solution removed in the underflow in association with every kilogram
of insoluble matter, k is given by:
2
k  0.7  0.5y s  3y s kg / kg
where ys is the concentration of the overflow solution in terms of mass fraction of solute
kg/kg. If the seeds are extracted with fresh solvent, how many ideal stages are
required?
4. How many stages are required for a 98 per cent extraction of a material containing 18 per
cent of extractable matter of density 2700 kg/m3 and which requires 200 volumes of liquid/100
volumes of solid for it to be capable of being pumped to the next stage? The strong solution is
to have a concentration of 100 kg/m3.
B. Equilibrium Stages Calculations

Extract Lean Solvent
V1, y1 Vn+1, yn+1
1 2 n–1 n
L0 , x 0 Ln , x n
Feed Leached Solids
Figure 9 Equilibrium stages for leaching processes
Assumptions:
1. Solid C is insoluble with solvent S
2. No solid in overflow
3. Steady-state operations L1 = L2 = Ln  L0; V1 V2 = Vn = Vn+1
Overall Material Balance: L0 + Vn+1 = V1 + Ln (21)
Solute Balance: L0 x 0 + Vn+1 yn+1 = V1 y1 + Ln xn (22)
Solving for yn+1:

1 V1y1  L 0 x 0
yn1  xn 
V1  L 0 Ln  L1  L 0
1
Ln
The operating line when plotted on anxy-diagram passes through the terminal points (x0, y1) and (xn,
yn+1).
Case 1: Amount of solution retained by inerts is constant

When the solution retained by the inerts is constant, both the underflow Ln and overflow Vn are
constant and the equation is a straight line.
The number of stages is given by the Kremser equations

log
y  y 
n1
*
n
N
y  y 
1
*
1
log
 yn1  y1
x n
*
 y1  (23)
* *
y1  x yn  xn
Since in leaching: 0
Therefore:
 yn1  xn 
log
N
 y1  x 0 
y  y 
log n1 1
 xn  x 0  (24)
Note:
The equation cannot be used for the entire extraction battery if L 0 differs from L1, L2, , Ln. In
this case, the compositions of all the streams entering and leaving the first stage are separately
calculated by a material balance, and then the equation is applied to the remaining
cascade.
Thus,
log
 yn1  xn 
N -1 
 y 2  x1 
 y  y2 
log n1
 xn  x1 (25)
Exercises 2:
1. A countercurrent extraction system is to treat 100 tons/h of sliced sugar beets with fresh water
as solvent. Analysis of the beets is as follows: water 48 %, sugar 12%, with balance pulp. If 97 %
sugar is to be recovered and the extract phase leaving the system is to contain 15 % sugar,
determine the number of cells required if each ton of the dry pulp retain 3 tons of solution.
2. Coconut oil is to be produced from dry copra in two stages. First, through expellers to squeeze
out part of the coconut oil and then through a countercurrent multistage solvent extraction.
After expelling, the dry copra cake contains 20 % residual oil. In the solvent extraction
operation, 90 % of the residual oil in the expeller cake is extracted as a solution containing 50
% by weight oil. If fresh solvent is used and 1 kg of solution with every 2 kg insoluble is removed
with underflow, how many ideal stages are required?
Case 2: Amount of solvent retained by inert is constant
' '
yn1  x n Y  Xn
log log n1
' '
y1  x 0 Y1  X0
N 
' ' Y Y
y y log n1 1
log n1 1
' ' Xn  X0
xn  x 0
(26)
where:
X = mass ratio of the solute to solvent in the underflow
Y = mass ration of the solute to solvent in the overflow
The above equation also needs the calculation of the first stage separately since the solvent content
of the fresh solids to the first stage is different from that in the other stages. Thus,
Yn1  Xn
log
Y2  X1
N -1 
Yn1  Y2
log
Xn  X1
(27)
Exercises 3
1. In exercises 2.1, determine the number of cells if each ton of dry pulp retains 3.5 tons of water.
(N = 19)
2. Roasted copper ore containing the copper as CuSO4 is to be extracted in a countercurrent

stage extractor. Each hour a charge consisting of 10 tons gangue, 1.2 tons CuSO4 and 0.5 tons
H2O is to be treated. The strong solution produced is to consist of 90 % H 2O and 10 % CuSO4 by
weight. The recovery of CuSO4 is to be 98 % of that in the ore. Pure water is to be used as fresh
solvent. After each stage, 1 on inert gangue retained 2 tons of water plus the copper dissolved
in that water. Equilibrium is attained in each stage. How many stages are required? (N = 10)
3. Powdered limestone (CaCO3) containing 10,000 ppm NaOH is to be washed in a two-step

continuous countercurrent washing system to remove most of the NaOH. Two cells are used
and 100,000 liters of water per 10 MT per day of limestone feed. The slurry discharge removed
from the underflow contains 0.091 MT of water per MT CaCO3. Assuming complete mixing and
washing in each cell, what will be the NaOH content of the washed and dried limestone in
ppm?
4. By extraction with kerosene, 2 tons of waxed paper per day is to be dewaxed in a continuous
countercurrent extraction system that contains a number of ideal stages. The waxed paper
contains, by weight, 25% paraffin wax and 75% paper pulp. The extracted pulp is put through
a dryer to evaporate the kerosene. The pulp, which retains the unextracted wax after
evaporation, must not contain over 0.2 lb of wax per 100 lb of wax-free pulp. The kerosene
used for the extraction contains 0.05 lb of wax per 100 lb of wax-free kerosene. Experiments
show that the pulp retains 2.0 lb of kerosene per lb of kerosene- and wax-free pulp as it is
transferred from cell to cell. The extract from the battery is to contain 5 lb of wax per 100 lb of
wax-free kerosene. How many stages are required?
C. Variable Underflow in Countercurrent Multistage Leaching
1. Ponchon-Savarit Method
Nomenclature:
C = inert material
A = extractable material
S = solvent
a = constant underflow
b = variable underflow
c = constant ratio solvent/inert material
DE = connode
E
F a
b
c
D 1
Figure 10 Graph of retention time vs composition for (a) constant underflow (b) variable
underflow (c) constant ratio solvent/inert material
inert material C
N 
extractable material  solvent AS (28)
A
X A  YA 
AS (29)
L = solution = extractable substance + solvent = B + C

N  L = amount of inert material A
L  X, L  Y = amount of extractable substance B
The material balances for the whole system are
L0 + Vn+1 = V1 + Ln = M (30)
L0 yA,0 + VN+1 yN+1,A = V1 y1,A + LN yN,A = MxM,A (31)
B = L0 N0  LN NN = MNM (32)
L0MVN+1 must lie on a straight line and LNMV1 must be another straight line. Usually the flows and
compositions of L0 and VN+1 are known and the desired exit concentration yA,N is set. Then the
coordinates NM and xAM can be determined.
In order to go stage by stage, we must derive the operating point equation, as we did for distillation
by Ponchon and Savarit method. Making a total balance on stage 1 and then on stage n.
Figure 11 Schematic Diagram of multi-stage countercurrent leaching process.

Retrieved from Ref [11]
L0 + V2 = V1 + L1 (33)
Ln-1 + Vn-1 = Vn + Ln (34)
The above equations can be rearranged as
L0  V1 = L1  V2   Ln  Vn-1 = Ln  Vn+1  
The coordinates of the operating point  can be obtained by a balance on solute A and the solid:
L0yA0  V1xA1 = ... = LNyAN  VN+1xA,N+1 = xA
B = L0N0 = ... = LNNN = N
Hence,
L 0 y A0  V1x A1 LNy AN  VN1x N+1
x AΔ   (35)
L 0  V1 LN  VN1
B L 0N0
NΔ   (36)
L 0  V1 L 0  V1
This point  can also be located graphically as the intersection of lines L0V1 and LNVN+1.
To graphically determine the number of stages, we start at L0 and draw a line L0 to locate V1. Then
an equilibrium tie line through V1 locates L1. Line L1 is drawn to give V2. A tie line from V2 gives L2. This
is continued until the desired LN is reached.
L5 L4 L3 L2
L1
V5 V4 V3 V2
Figure 12 Ponchon-Savarit Diagram.

Exercises 4
A. Single Step Extraction
1. In a single step solid-liquid extraction soybean oil has to be extracted from soybean flakes using
hexane as solvent. 100 kg of the flakes with an oil content of 20 wt% are contacted with 100
kg fresh hexane. 1.5 kg of inert material holds back a constant value of 1 kg solution.
Determine in the Ponchon - Savarit diagram the amount and composition of the flows
leaving the extraction plant.
B. Continuous Countercurrent Solid - Liquid Extraction

1. A continuous countercurrent multistage system is to be used to leach oil from meal by benzene
solvent. The process is to treat 1000 kg/h of inert solid meal (B) containing 400 kg oil (A) and
also 25 kg benzene (C). The inlet flow per hour of fresh solvent mixture contains 655 kg benzene
and 10 kg oil. The leached solids are to contain 60 kg oil. Settling experiments similar to those
in the actual extractor show that the solution retained depends on the concentration of oil in
the solution. The data are tabulated below as N kg inert solid B/kg solution and yA kg oil A/kg
solution.
N 2.00 1.98 1.94 1.89 1.82 1.75 1.68 1.61

YA 0 0.1 0.2 0.3 0.4 0.5 0.6 0.7
Calculate the amounts and concentrations of the stream leaving the process and the number
of stages required
2. 10.000 kg of wet sugar beet chips with a composition of 28 wt% water, 32 wt% sugar and 40
wt% inert material have to be extracted in a continuous countercurrent extraction plant using
hot water as solvent. The produced extract must contain 40 wt% sugar and the total extraction
efficiency for sugar has to be 90%. 1 kg inert material retains 3 kg solution and this value is
constant.
Determine in the Ponchon - Savarit diagram the number of ideal steps for this separation
problem.
3. Barium sulfide is produced by reacting barium sulfate ore with coal. The result is barium black
ash, which is BaS plus insoluble solids. Since BaS is soluble in water, it can be leached out with
water. In thickeners the insoluble solids in the underflow typically carry with them 1.5 kg liquid
per kg insoluble solids. At equilibrium the overflow and underflow liquids have the same BaS
concentrations (Treybal, 1980). We want to process 350 kg/h of insoluble solids plus its
associated underflow liquid containing 0.20 mass fraction BaS. Use a countercurrent system
with 2075 kg/h of water as solvent. The entering water is pure. We desire the outlet underflow
liquid to be 0.00001 mass fraction BaS. Find:
a. The BaS mass fraction in the exiting overflow liquid.
b. The number of equilibrium stages required.
4. It is desired to extract the oil from halibut livers by countercurrent extractor system with ethyl
ether. The quantity of solution retained by the granulated liver has been determined
graphically as a function of composition of the solution as given. The fresh halibut livers contain
25.7 mass % oil. If 95 % of the oil is to be extracted and the final solution obtained from the
operation is to contain 10 mass % oil, compute:
a. Pounds of oil-free ether required per 1000 lbs of fresh livers charges
b. Quantity and composition of the discharged solids
c. Number of ideal stages
d. Number of actual stages if the efficiency is 70 %
Solution concentration
0 0.10 0.20 0.30 0.40 0.50 0.60 0.65 0.70 0.72
(lbs oil/lbs solution)
Retention
(lbs solution 0.205 0.242 0.286 0.339 0.405 0.484 0.60 0.672 0.765 0.810
retained/lbs solid)
2. McCabe-Thiele method
The number of ideal stages for variable underflow can also be determined by the McCabe-Thiele
method.
The terminal points on the operating line are determined using the material balances. Normally only
one intermediate point is required to draw the operating line unless there is a large change in L and
V or the operating line is very close to the equilibrium line.
To locate the intermediate point of the operating line, choose a yn value of about (y0 + yN)/2 to fix Ln,
Vn+1 xn+1 and are calculated from
Vn1  Ln  V1  L 0 (37)
Ln V1x1  L 0 y 0
x n1  yn  (38)
Vn1 Vn1
This point (yn, xn+1) together with the two terminal points (y0, x1) and (yN, xN+1) are used to draw the
operating curve. The McCabe-Thiele method is used to determine the number of ideal stages by
counting the number of triangles between the equilibrium and curved operating lines in the x-y
diagram.
Exercises 5.
1. Oil is to be extracted from 10,000 lb/h of granulated halibut livers, based on oil-free livers, which
contain 0.043 gal of extractable oil per lb of oil-free livers. It is desired to extract 95% of the oil
in a countercurrent extraction system using oil-free diethylether as solvent. The final extract is
to contain 0.65-gal oil per gal of extract. Assume volumes of oil and ether are additive and
that leaching will be completed in one stage. Ravenscroft’s underflow data show scatter, so
use the following smoothed data to predict underflow rates:
Gal Liquid
Gal Oil per Gal Retained per lb
Liquid Oil-Free Livers
0.00 0.035
0.10 0.042
0.20 0.049
0.30 0.058
0.40 0.069
0.50 0.083
0.60 0.100
0.70 0.132
Determine the number of ideal stages required.
VI. WASHING
Washing is almost identical to extraction, the main distinction being one of the emphases in that in
washing the inert material is the required product, and the solvent used is water which is cheap and
readily available. Various washing situations are encountered and can be analyzed. That to be
considered is one in which a solid precipitate, the product, retains water which also contains residues
of the mother liquor so that on drying without washing these residues will remain with the product. The
washing is designed to remove them, and examples are butter and casein and cheese washing in
the dairy industry.
Calculations on counter current washing can be carried out using the same methods as discussed
under extraction, working from the operating and equilibrium conditions. In washing, fresh water is
often used for each stage and the calculations for this are also straightforward.
In multiple washing, the water content of the material is xw (weight fraction) and a fraction of this, x, is
impurity, and to this is added yxw of wash water and after washing thoroughly, the material is allowed
to drain. After draining it retains the same quantity, approximately, of water as before, xw. The residual
yxw of wash liquid, now at equilibrium containing the same concentration of impurities as in the liquid
remaining with the solid, runs to waste. Of course in situations in which water is scarce counter current
washing may be worthwhile.
The impurity which was formerly contained in xw of water is now in a mass (xw + yxw): its concentration
x has fallen by the ratio of these volumes, that is to x [xw/(xw + yxw)].
So the concentration remaining with the solid after one washing, x1, is given by:
x1 = x[xw /xw(1 + y)] = x[1/(1 + y)]

After two washings:
x2 = x1[1/(1 + y)] = x[1/(1 + y)]2
And so after n washings:
n
 1 
xn  x    (39)
 1 y 
If, on the other hand, the material is washed with the same total quantity of water as in the n washing
stages, that is nyxw, but all in one stage, the impurity content will be:
'  1 
xn  x    (40)
 ny  1
It is clear that the multiple contact washing is very much more efficient in reducing the impurity
content that is single contact washing, both using the same total quantity of water.
Example
After precipitation and draining procedures, it is found that 100 kg of fresh casein curd has a liquid
content of 66% and this liquid contains 4.5% of lactose. The curd is washed three times with 194 kg of
fresh water each time. Calculate the residual lactose in the casein after drying. Also calculate the
quantity of water that would have to be used in a single wash to attain the same lactose content in
the curd as obtained after three washings. Assume perfect washing and draining of curd to 66% of
moisture each time.
Solution:
100 kg of curd contain 66 kg solution. The 66 kg of solution contain 4.5% that is 3 kg of lactose.
In the first wash (194 + 66) = 260 kg of solution contain 3 kg lactose.

In 66 kg of solution remaining there will be (66/260)  3 = 0.76 kg of lactose.
After the second wash the lactose remaining will be (66/260)  0.76 = 0.19kg
After the third wash the lactose remaining will be (66/260)  0.19 = 0.048 kg
Or, after three washings lactose remaining will be 3  (66/260)3 = 0.048 kg as above
So, after washing and drying 0.048 kg of lactose will remain with 34 kg dry casein so that
Lactose content of the product = 0.048/34.05

= 0.14%
And total wash water = 3  194 = 582 kg
To reduce the impurity content to 0.048 kg in one wash would require x kg of water, where
(3  66)/(x + 66) = 0.048 kg
x = 4060 kg
And so the total wash water = 4060 kg
Alternatively using equations (39) and (40)

xn = x[1/(1 + y)]n
= 3[1/(1 + 194/66)]3
= 0.049
xn' = x[1/(ny+ 1)]
0.049 = 3[1/(ny+ 1)]

ny = 61.5.
Total wash water = nyxw = 61.5 x 66

= 4060 kg
Exercises 6
1. Casein is to be washed, in a multistage system, by water. The casein curd has initially a water
content of 60% and between stages it is drained on an inclined screen to 80% water (both on
a wet basis). The initial lactose content of the casein is 4.5 % on a wet basis, and it is necessary
to produce casein with a lactose content of less than 1 % on a dry basis. How many washing
steps would be needed if the wet casein is washed with twice its own weight of fresh water in
each step?
2. We plan to wash dilute sulfuric and hydrochloric acids from crushed rock in a counter current
system. Operation is at 25°C and one atmosphere. 100.0 m3/day of wet rock are to be washed.
After settling, the porosity is constant at 0.40. Thus, the underflow rate is 40.0 m3/day. The initial
concentration of the underflow liquid is 1.0 kg sulfuric acid/m3 and 0.75 kg hydrochloric
acid/m3. We desire an outlet underflow sulfuric acid concentration of 0.09 kg/m3. The wash
liquid (overflow) rate is 50.0 m3/day, and the inlet wash water is pure. For these dilute solutions
assume that the solution densities are constant, and are the same as pure water, 1000.0 kg/m3.
Find:
a. The number of equilibrium stages required
b. The outlet concentration (kg/m3) of hydrochloric acid in the underflow liquid
3. A washing operation is processing 10,000 kg/h of wet solids. The liquid is essentially water with
a density of 1000.0 kg/m3, the dry solids have a density of 1500.0 kg/m3, and the porosity (also
known as the volume fraction of void space) is measured as ε = 0.40. What is the flow rate of
the underflow liquid in kg/h.
Extraction and Washing Equipment

The first stage in an extraction process is generally mechanical grinding, in which the raw material is
shredded, ground or pressed into suitably small pieces or flakes to give a large contact area for the
extraction. In some instances, for example in sugar-cane processing and in the extraction of
vegetable oils, a substantial proportion of the desired products can be removed directly by expression
at this stage and then the remaining solids are passed to the extraction plant. Fluid solvents are easy
to pump and so overflows are often easier to handle than underflows and sometimes the solids may
be left and solvent from successive stages brought to them.
This is the case in the conventional extraction battery. In this a number of tanks, each suitable both for
mixing and for settling, are arranged in a row or a ring. The solids remain in the one mixer-settler and
the solvent is moved progressively round the ring of tanks, the number, n, often being about 12. At any
time, two of the tanks are out of operation, one being emptied and the other being filled. In the
remaining (n – 2), tanks extraction is proceeding with the extracting liquid solvent, usually water, being
passed through the tanks in sequence, the "oldest" (most highly extracted) tank receiving the fresh
liquid and the "youngest" (newly filled with fresh raw material) tank receiving the most concentrated
liquid. After leaving this "youngest" tank, the concentrated liquid passes from the extraction battery to
the next stage of the process. After a suitable interval, the connections are altered so that the tank
which has just been filled becomes the new “youngest" tank. The former "oldest" tank comes out of
the sequence and is emptied, the one that was being emptied is filled and the remaining tanks retain
their sequence but with each becoming one stage "older". This procedure which is illustrated in Fig. 13
in effect accomplishes counter current extraction, but with only the liquid physically having to be
moved apart from the emptying and filling in the terminal tanks.
Figure 13 Extraction batteries

In the same way and for the same reasons as with counter flow heat exchangers, this counter current
(or counter flow) extraction system provides the maximum mean driving force, the log mean
concentration difference in this case, contrasting with the log mean temperature difference in the
heat exchanger. This ensures that the equipment is used efficiently.
In some other extractors, the solids are placed in a vertical bucket conveyor and moved up through
a tower down which a stream of solvent flows. Other forms of conveyor may also be used, such as
screws or metal bands, to move the solids against the solvent flow. Sometimes centrifugal forces are
used for conveying, or for separating after contacting.
Washing is generally carried out in equipment that allows flushing of fresh water over the material to
be washed. In some cases, the washing is carried out in a series of stages. Although water is cheap, in
many cases very large quantities are used for washing so that attention paid to more efficient washing
methods may well be worthwhile. Much mechanical ingenuity has been expended upon equipment
for washing and many types of washers are described in the literature.
References:
[1] Earle, R. L. (2013). Unit Operations in Food Processing. Elsevier, Technology and Engineering.
[2] Geankoplis, C. J. (1993). Transport Processes and Unit Operations, 3rd Edition. Prentice-Hall
International, Inc.
[3] McCabe et al. (1993). Unit Operations of Chemical Engineering, 5th Edition. McGraw-Hill, pp.
614-623.
[4] McCabe et al. (2001). Unit Operations of Chemical Engineering, 6th Edition. McGraw-Hill, pp.
742-47.
[5] Richardson et al. (2002). Coulson & Richardson's Chemmical Engineering Volume 2: Particle
Technology and Separation Processes, 5th Edition. Oxford: Butterworth Heinemann.
[6] Seader, J.D. & Henley, E. J. (1998). Separation Process Principles. John Wiley, pp. 198-201.
[7] Treybal, R.E. (1987). Mass-Transfer Operations, 3rd Edition. McGraw-Hill, (reissue), pp. 717-761.
[8] Wankat, P. C. (2012) Separation Process Engineering – 3rd Edition. Pearson Education, Inc.
[9] http://www.gunt.de/images/download/extraction_english.pdf
[10] http://studenti.di3.units.it/Impianti%20chimici/04%20Script%20Examples%20Solid%20Liquid%20
Extraction.pdf
[11] http://kexhu.people.ust.hk/ceng3210/221-07.pdf
[12] http://fcee.utm.my/abbas/files/2016/06/Leaching.pdf

Extraction Method

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Lecture Notes 11 - Solid-Liquid Extraction 1

Engr. Caesar P. Llapitan

Typical users include:

II. FACTORS INFLUENCING THE RATE OF EXTRACTION

There are four important factors to be considered:

4. Agitation of the fluid

III. LIQUID-SOLID EQUILIBRIUM

Liquid-solid phase equilibrium is important in understanding leaching, crystallization, and adsorption.

Flow through a leaching system may be crosscurrent or countercurrent.

0  Vn1yn1  Vaya  Lax a  Lnx n (2)

The operating equation is obtained by rearranging the component balance:

Vn1yn1  Vaya  Lax a  Lnxn (3)

Two main types of calculations are usually performed:

Constant Solution Underflow

For leaching, the equilibrium line is xe = ye, so the equation becomes:

Variable Solution Underflow

The "P point" is used in the constructions. It is given by the equations:

P represents the "net flow" of material through the system, so that

V. EXAMPLES SOLID-LIQUID EXTRACTION

A. Rectangular Triangle Diagram Method

Figure 2 Rectangular Triangle Diagram

Figure 3 Control volume for material balance in leaching process

Overall Material Balance F = V +L (10)

Component Balance FxF = Vy V + Lx L (11)

Locus of the Overflow

Equation of a straight line: xS or yS

Thus, the locus of the underflow is parallel to the hypotenuse

Equation of a straight line:

Determining the Number of Stages Figure 6 Case 3 right triangular diagram

V1, y1 Vn+1, yn+1

Overall material balance: L0 + Vn+1 = V1 + Ln (16)

Component balance: L0 x 0 + Vn+1 yn+1 = V1 y1 + Ln xn (17)

Let J = addition point: J = L0 + Vn+1 = V1 + Ln (18)

If we let P = difference point

Procedure in determining the number of stages:

Exercises 1: Retrieved from Ref [5]

B. Equilibrium Stages Calculations

Figure 9 Equilibrium stages for leaching processes

Overall Material Balance: L0 + Vn+1 = V1 + Ln (21)

Solute Balance: L0 x 0 + Vn+1 yn+1 = V1 y1 + Ln xn (22)

Solving for yn+1:

Case 1: Amount of solution retained by inerts is constant

The number of stages is given by the Kremser equations

Case 2: Amount of solvent retained by inert is constant

Y = mass ration of the solute to solvent in the overflow

2. Roasted copper ore containing the copper as CuSO4 is to be extracted in a countercurrent

3. Powdered limestone (CaCO3) containing 10,000 ppm NaOH is to be washed in a two-step

C. Variable Underflow in Countercurrent Multistage Leaching

L = solution = extractable substance + solvent = B + C

The material balances for the whole system are

L0 yA,0 + VN+1 yN+1,A = V1 y1,A + LN yN,A = MxM,A (31)

Figure 11 Schematic Diagram of multi-stage countercurrent leaching process.

Ln-1 + Vn-1 = Vn + Ln (34)

The above equations can be rearranged as

L0yA0  V1xA1 = ... = LNyAN  VN+1xA,N+1 = xA

B = L0N0 = ... = LNNN = N

Figure 12 Ponchon-Savarit Diagram.

B. Continuous Countercurrent Solid - Liquid Extraction

N 2.00 1.98 1.94 1.89 1.82 1.75 1.68 1.61

Determine the number of ideal stages required.

x1 = x[xw /xw(1 + y)] = x[1/(1 + y)]

After two washings: