Separation

Processes II

Engr. Ajibola T. Ogunbiyi

SOLID-LIQUID EXTRACTION

LEACHING

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Recommended Texts:
1. Treybal, R. E. (1980). Mass-Transfer Operations. Singapore: McGraw-
Hill.
2. McCabe, W. L., Smith, J. C., and Harriot, P. (1993). Unit Operations of
Chemical Engineering. Singapore: McGraw-Hill
3. Geankoplis, C. J. (1993). Transport Processes and Unit Operations
(3rd Edition). New Jersey, USA: Prentice-Hall International Inc.
4. Coulson, J.M. and Richardson, J.F. (2002). CHEMICAL ENGINEERING,
Volume II. Fifth Edition. Particle Technology and Separation Processes.
Published by Butterworth-Heinemann

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Module Content
Introduction
Principles of leaching
Examples of leaching in the industry
Rate of Leaching
Methods of Operation and Equipment types
Unsteady-state Operation
Steady-state (Continuous) Operation
Methods of Calculation
Stage efficiency
Practical equilibrium
Single-stage leaching
Multistage Crosscurrent leaching
Multistage Countercurrent leaching
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Methods of Calculation

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Methods of calculation
It is important to be able to calculate the extent of leaching
which can be obtained for a given procedure, i.e., to calculate
the amount of soluble substance leached from a solid,
knowing the following:

(i) The initial solute content of the solid

(ii) The number and amount of washings with leaching solvent
(iii)The concentration of solute in the leaching solvent, if any,
and
(iv)The method, whether batch or continuous countercurrent
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Alternatively, there may be a need to compute the number of
washings, or number of stages, required to reduce the solute
content of the solid to some specified value, knowing:

(i) The amount the leaching solvent.

(ii) The solute concentration in the leaching solvent

The method are very similar to those used for liquid

extraction.

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 Concepts of a stage of extraction and stage
efficiency
What constitutes a single stage of extraction?
Consider a simple batch leaching operation where the following takes
place:
(i) The solid is leached with sufficient amount of solvent to dissolve all the
soluble solute.
(ii) There is no preferential adsorption of either solvent or solute by the
solid.
(iii) There is adequate time of contact of solid and solvent.
(iv) All the solute will be dissolved.
The mixture is then a slurry of insoluble solid immersed in a solution of
solute in the solvent. The insoluble phases are then separated physically by
settling, filtration, or drainage, and the entire operation constitutes one
stage.
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What is 100 percent stage efficiency?
If the mechanical separation between the solid and
liquid were perfect, there would be no solute
associated with the solid leaving the operation and
complete separation of solute and insoluble solid
would be accomplished in a single stage. This would
be an equilibrium stage of 100 percent stage
efficiency.

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In reality, stage efficiencies are less than 100% because:

(i) Inadequate contact time may make the solute only partially
dissolved in the solvent.

(ii) Separation between the insoluble solid and the solution

cannot be perfect, as the solid will always retain some solute
with it.

Either or both of these will result in lowered stage efficiency.

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Practical Equilibrium
Leaching calculations, like other mass-transfer operation, are generally
most conveniently carried out using graphical representations. These
will require representing equilibrium conditions on a graph.

It is simplest to use real or practical equilibrium conditions which take

stage efficiencies into account directly, similar to the cases of gas
absorption and distillation.

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Three-component systems are dealt with in the simplest cases.
The following give the notations commonly used:
A = Pure solvent
B = Insoluble carrier solid
C = Soluble solute
Note the above convention, as this will be stuck with throughout this
module.

A rectangular coordinate system is preferred to the triangular, as

the latter usually involves crowding of the construction lines into
one corner of the diagram.
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Let
𝑚𝑎𝑠𝑠 𝐵
N = Concentration of insoluble solid B in any mixture =
𝑚𝑎𝑠𝑠 (𝐴+𝐶)
whether the solid is wet with liquid solution or not.

𝑥 and 𝑦 = solute C compositions in weight fraction on a B-free basis

𝑥 = wt. fraction C in the effluent solution from a stage (B-free basis)

𝑚𝑎𝑠𝑠 𝐶
= in the effluent solution
𝑚𝑎𝑠𝑠 (𝐴+𝐶)

𝑦 = wt. fraction C in the solid or slurry (B-free basis)

𝑚𝑎𝑠𝑠 𝐶
in the slurry
𝑚𝑎𝑠𝑠 (𝐴+𝐶)
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Special cases:
(1)If the solid is dry (for example, as it is before leaching)
𝑚𝑎𝑠𝑠 𝐵 𝑚𝑎𝑠𝑠 𝑜𝑓 𝑖𝑛𝑠𝑜𝑙𝑢𝑏𝑙𝑒
𝑚𝑎𝑠𝑠 𝐴 = 0, and 𝑁 = =
𝑚𝑎𝑠𝑠 𝐶 𝑚𝑎𝑠𝑠 𝑜𝑓 𝑠𝑜𝑙𝑢𝑏𝑙𝑒
𝑚𝑎𝑠𝑠 𝐶
𝑦= 𝑚𝑎𝑠𝑠 (𝐴+𝐶)
= 1.0 (since mass A = 0)

(2) For pure solvent A, 𝑁 = 0 (i.e. no insoluble solid)

𝑥 = 0 (i.e. no solute, C = 0)
𝑚𝑎𝑠𝑠 𝐶
as 𝑥 =
𝑚𝑎𝑠𝑠 (𝐴+𝐶)
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 Representing concentrations in leaching and washing on a
coordinate system
Consider a simple case of a mixture of insoluble solid from which all the
solute has been leached, suspended in a solution of the solute in a solvent,
as represented by point 𝑀1 on the above figure.
Concentration of the clear solution = 𝑥
Concentration of the insoluble solid/solution (B-free basis) = 𝑁𝑀1
Let the insoluble solid be non-adsorbent
If the mixture has adequate time for settling, and the clear liquid is drawn
off, the remaining sludge will be made of the insoluble solid suspended in
a small amount of the solution.

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Figure: Concentrations in leaching and washing
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Let the clear liquid be 𝑅1 (note that at 𝑅1 , 𝑁𝑅1 = 0 since it’s a clear liquid)
The remaining sludge = 𝐸1
The composition of the solution in the sludge will be the same as that of
the clear liquid withdrawn, i.e. 𝑦 ∗ = 𝑥
Concentration of solid B in the sludge 𝐸1 = 𝑁𝐸1
The value of 𝑁𝐸1 is a function of the length of time 𝜃1 allowed for settling

Hence, we can say

𝑀1 = mixture of leached solid and solution of the solute in a solvent
𝑅1 = clear solution drawn off the insoluble solid
𝐸1 = slurry in a small amount of solution
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• Line 𝐸1 𝑅1 is a vertical tie line joining the points representing
the two effluent streams, i.e. clear liquid and slurry.

• If the circumstances described are maintained in an actual

leaching, points 𝐸1 and 𝑅1 can be taken as the practical
conditions of equilibrium for that leaching.

• Usually in practice, sufficient time of settling is not allowed,

and in that case, the sludge will be less concentrated in
insoluble solids. In this case, the sludge could be represented
by point 𝐸 ′1 , lower than 𝐸1 .

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A point 𝑅2 , slightly above the clear solution line (𝑁𝑀 = 0) and
from another mixture 𝑀2 settled for time θ1 with a
corresponding sludge 𝐸2 , can result if there is any of the
following circumstances:
(1.) If the solid does not settle well to give an absolutely clear
solution.

(2) If a small amount of solid is carried with the withdrawn

solution

(3) If solid B dissolves to a small extent in the solution

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Types of Possible Equilibrium curves

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Type 1: Figure (a) represents data obtained for cases where solute 𝐶 is
infinitely soluble in solvent 𝐴, so that 𝑥 and 𝑦 may have values over
the entire range from 0 to 1.0. The curve DFE represents the
separated solid under real conditions expected in practice. Curve GHJ
represents the withdrawn solution and lies above the line 𝑁 = 0
because of the reasons earlier mentioned.

The tie line (e.g. 𝐹𝐻) are not vertical because of the following reasons:
(1) In adequate time of contact of the mixture with the solvent
(2) Occurrence of preferential adsorption of the solute on the solid
(3) The solubility of the solute in the solid B
All these make the solute C distribute unequally between the liquid
and solid phases at equilibrium. Here, 𝑦 > 𝑥 Engr. A. T. Ogunbiyi
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CHE320
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Type 1 Equilibrium curve

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Type 2
Figure (b) a case where no absorption of solute occurs, so that
the withdrawn solution and the solution associated with the
solid have the same consumption, making the tie lines
vertical. Here 𝑦 ∗ = 𝑥, as seen in the projection of 𝑥 and 𝑦 in
the plot below the upper diagram.
This results in an 𝑥𝑦 curve in the lower figure identical ith ∗the
45o line, and a distribution coefficient 𝑚, defined as 𝑦 Τ𝑥,
equals unity.

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Type 2 equilibrium curve

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Constant underflow
This is a case where the solids are settled or drained to the same
extent at all concentrations. This is why the line KL is horizontal
in figure (b). This occurs when the density and viscosity of the
solution (which both determine the settling characteristics of the
solid in the slurry) do not change at all solute concentrations.
The opposite of this situation is variable underflow.
In constant underflow, the solution contains no substance B,
either dissolved or suspended, the reason line 𝑁 vs 𝑥 coincides
with the line 𝑁 ≠ 0.
It is possible to regulate the operation of continuous thickeners o
that this will occur.
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Type 3
Figure (c) represents a case where solute 𝐶 has a limited solubility
𝑥𝑠 in solvent 𝐴. No matter the concentration of the solute in the
slurry phase, beyond the particular solubility called saturation
concentration, 𝑥𝑠 , the concentration of the solute in the clear
solution after settling does not increase. No clear solution stronger
than 𝑥𝑠 can be obtained, so that the tie lines joining slurry and
saturated solution must converge, as shown.
Since the tie lines to the left of PS are shown vertical, it means no
adsorption occurs, and overflow liquids are clear.

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Type 3 Equilibrium curve

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 SINGLE STAGE LEACHING

Single stage leaching or washing Engr. A. T. Ogunbiyi CHE320

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Consider the single real leaching or washing stage of the Figure above.
Let the circle represent the entire operation, including mixing of solid
and leaching solvent and mechanical separation of the resulting
insoluble phases by whatever means may be used.

Let the 𝐵 discharged in the leached solids be taken as the same as that
in the solids to be leached.

Making a material balance for the insoluble solid B

𝐵 in Feed = 𝐵 in leached solids/slurry
𝐵 = 𝑁𝐹 𝐹 = 𝐸1 𝑁1 −−−−−−−− − (1)
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A solute (𝐶) balance gives:
𝐹𝑦𝐹 + 𝑅0 𝑥0 = 𝐸1 𝑦1 + 𝑅1 𝑥1 −−−−−−− − (2)

A solvent (𝐴) balance gives

𝐹(1 − 𝑦𝐹 ) + 𝑅0 1 − 𝑥0 = 𝐸1 1 − 𝑦1 + 𝑅1 1 − 𝑥1 −− − 3

Carrying out an overall balance (on a B-free basis)

𝐹 + 𝑅0 = 𝐸1 + 𝑅1 = 𝑀1 −−−−−−− − 4

Where 𝑀1 = mixture of the solids to be leached and the leaching

solvent on a B-free basis
Note that B-free basis means only the “solution” is considered where
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Concentration of insoluble solid 𝐵 in the mixture 𝑀1 (𝐵 -free) is

𝐵 𝐵
𝑁𝑀1 = = −−−−− − 5
𝐹 + 𝑅0 𝑀1

And Concentration of the solute in the slurry is:

𝑦𝐹 𝐹 + 𝑅𝑜 𝑥𝑜
𝑦𝑀1 = −−−−−−− − 6
𝐹 + 𝑅𝑜

These relations can be shown on the coordinate system of the following

figure.
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 Point 𝐹 represents the solids to the leached
𝑅𝑜 represents the leaching solvent
𝑀1 = overall mixture (𝑀1 must fall on the straight line
joining 𝑅𝑜 and 𝐹)

Points 𝐸1 and 𝑅1 , representing the effluent streams, are located

at opposite end of the tie line (𝐸1 𝑅1 ) through 𝑀1 , and their
composition can be read from the diagram.

Equation (1) can be used for the calculation of 𝐸1 and Eq. (4) for
𝑅1 .
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 Single leaching or washing
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Example
Multistage crosscurrent leaching
If the leached solids from a single stage leaching is contacted
with a fresh batch of leaching solvent, additional solute can be
dissolved or washed away from the insoluble material. The
calculations for additional stages are merely repetitions of the
procedure for a single stage, with the leached solids from any
stage becoming the feed solids to the next stage. Equations (1)
to (6) apply, with only obvious changes in the subscripts to
indicate the additional stages. The situation described forms
the basis of a multistage crosscurrent leaching.
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Example
Caustic soda is being made by treatment of slaked lime, Ca(OH)2, with a
solution of sodium carbonate. The resulting slurry consists of particles
of calcium carbonate, CaCO3, suspended in a 10% solution hydroxide,
NaOH, 0.125kg suspended/kg solution. This is settled, the clear odium
hydroxide solution withdrawn and replaced by an equal weight of
water, and the mixture thoroughly agitated. After repetition of this
procedure (a total of two freshwater washes), what fraction of the
original NaOH in the slurry remains unrecovered and therefore lot in
the sludge? The settling characteristics of the slurry, determined under
conditions representing the practice to be followed in the process,
show adsorption of the solute on the solid.
Multistage countercurrent leaching

A process flowsheet for Multistage countercurrent leaching or washing

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The ideal stages are numbered in the direction of the solids or
underflow stream.
The solvent-solute phase or R phase is the liquid phase that
overflows continuously from stage to stage countercurrently to
the solid phase, dissolving the solute as it moves along.
The slurry phase E composed of inert solids (B) and a liquid
phase of A and C is the continuous underflow from each stage.
Note that the composition of the R phase is denoted by 𝑥 while
that of E phase is 𝑦.

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Assumptions:
1. The solid B is insoluble and is not lost in the liquid R phase
2. The flowrates of the solids is constant throughout the cascade of
stages
3. As in single-stage leaching, R is kg/hr of overflow solution and E is
kg/hr of liquid solution in the slurry retained by the slurry.
To derive the operating line equation, an overall balance and a
component balance of solute C is made over the first n stages.
A solution (A+C) balance for the entire plant is:
𝐹 + 𝑅𝑁𝑝 +1 = 𝑅1 + 𝐸𝑁𝑝 = 𝑀 -------------------------------- (7)
And a solute (C) balance is:
𝐹𝑦𝐹 + 𝑅𝑁𝑝 +1 𝑥𝑁𝑝+1 = 𝑅1 𝑥1 + 𝐸𝑁𝑝 𝑦𝑁𝑝 = 𝑀𝑦𝑀 −−−− −(8)

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M represents the hypothetical B-free mixture obtained by mixing solids to
be leached and leaching solvent. See the figure below for the operating
diagram for the plant.

The coordinates of point M are:

𝐵
𝑁𝑀 = −−−−−−− −(9)
𝐹 + 𝑅𝑁𝑝+1

𝐹𝑦𝐹 + 𝑅𝑁𝑝+1 𝑥𝑁𝑝+1

𝑦𝑀 = −−−−−− −(10)
𝐹 + 𝑅𝑁𝑝+1
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The points 𝐸𝑁𝑝 and 𝑅1 , representing the effluents from the cascade,
must lie on a line passing through M, and 𝐸𝑁𝑝 will be on the
“practical” equilibrium curve.

Equation (7) can be rearranged as:

𝐹 − 𝑅1 = 𝐸𝑁𝑝 − 𝑅𝑁𝑝+1 = ∆𝑅 −−−− − 11

Similarly, a solution balance about any number of stages, such as the

first three can be arranged in this form:

𝐹 − 𝑅1 = 𝐸3 − 𝑅4 = ∆𝑅 −−−− − 12

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