Separation Process Fundamentals H81SPF

Leaching and Washing

1.0 Introduction

Leaching and Washing are extraction processes concerned with the removal of material
(solute) from a solid using a liquid (solvent). The valuable product may be the material
which is removed or the solid which remains. The solute may be solid or liquid. For
leaching, solute is within the solid particles. For washing, solute is on the surface of the solid
particles. Operation can be batchwise or continuous.

Examples:

Extraction of gold from ore using aqueous cyanide solution

Extraction of oil from seeds using oil solvent
Extraction of sugar from sugar cane/beet using water
Extraction of toxic material from mine tailings into groundwater using rainfall

Extraction is controlled by the rate of mass transfer of the solute from the solid to the bulk
solution. There are three steps in the path of the solute from the solid out into the bulk
solvent:

1. Dissolution of solute into solvent (involves change of phase or chemical reaction)

2. Diffusion of solute through pores in solid particle
3. Diffusion of solute from particle surface out into bulk solution

For washing, step 2 is non-existent.

2.0 Process Parameters and Equipment

Choice of process parameters and equipment depends on which step is the rate-controlling
step.

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 Separation Process Fundamentals H81SPF

There are four main process parameters which can be varied:

Solid particle size - Smaller particles give shorter path for solute within particle pores and a
greater surface area for removal into bulk solution (important if step 2 is the rate-controlling
step). However, separation of particles from liquid solvents and percolation of solvent
between particles is more difficult for smaller particles.
Other notes: Particle size range should be small so that extraction times for each particle are
similar. Particles may break up during processing (prior crushing may not be necessary). If
solute particle size is very small and highly disseminated within solid particle, small particle
size is important.

Solvent - Properties of solvent are selective for the operation.

Agitation - Increasing agitation improves transfer of solute from particle surface to bulk
solution (important if step 3 is the rate-controlling step). Increasing agitation can also keep
particles suspended.

Temperature - Increasing temperature usually increases reaction and diffusion rates, and
reduces solvent viscosity, which all increase rate of extraction. For extraction of substance
from plant materials, high temperatures can be undesirable.

Coarse particles are treated in fixed beds by percolation methods. Finer particles can be
suspended in solution and are treated as a suspension which is agitated. Equipment is
batchwise or continuous.

Solution Mining - circulation of solvent through an ore body to remove soluble species.

Percolation tanks - Solid is loaded into tank which has a perforated base. Solvent is added
which immerses the solid and percolates down and out of the tank through holes in the base.
Particle size range should be small to increase voidage therefore reducing pressure drop
required for flow, and also reducing channelling. Solvent can be pumped through in closed
vessels (diffusers). This constitutes one stage. An alternative is to continuously add and
remove solvent.

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 Separation Process Fundamentals H81SPF

Agitation vessels - Solid is loaded into tank which has a filter at the base. Solvent is added
and the mixture is agitated by either mechanical impellers or injection of a gas (air). At
duration of leaching, agitation ceases, solids settle and clear liquid is siphoned off the top.
This constitutes one stage. There will be solvent retained between the settled particles,
particularly for very fine particles. Can have a series of wash stages where fresh solvent is
added and the solids are allowed to settle, or can have a filter or thickener.

Thickener - Operated continuously. The slurry from the agitator is added through the top
centre of the thickener such that it does not mix with the clear liquid at the top. The solid
settles and is directed out through a central base cone by a slowly rotating rake. Clear liquid
is siphoned off the top.

Fig. 1: Dorr Agitator Fig. 2: Dorr Thickener

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 Separation Process Fundamentals H81SPF

Classifier - Usually used for washing coarse solids. Tank has a sloping bottom. The particles
are scooped out of the mixture by rakes which carry them upwards and out the top of the tank.
The liquid level increases and is decanted from the deep end of the tank.

Fig. 3: Dorr Classifier

Extractors - various leaching devices used in the seed industry.

Rotocel - Counter-current arrangement. Tank is split into a number of wedge-shaped

compartments. Seeds are added to each compartment and the tank rotates. Solvent is sprayed
over the seeds which percolate down through a perforated base and pumped to the next
compartment. Once the seeds have completed one revolution, they are dumped.

Bollman - Solids are contained in perforated baskets which are attached to a conveyor. They
descend on one side (co-current extraction) and ascend on the other (counter-current
extraction).

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 Separation Process Fundamentals H81SPF

Fig. 4: Rotocel

Fig. 5: Bollman Extractor

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 Separation Process Fundamentals H81SPF

concentration gradient
3.0 Mass Transfer: (departure from equilibrium)

driving force
rate of mass transfer
resistance

z
Turbulent
Laminar - molecular diffusion

CS

Fig. 6: Mass transfer from surface into bulk

C A
For molecular diffusion, Ficks law, J A DAB
z

JA = diffusional flux of component A (moles/area.time).

DAB = diffusivity of A into B (area/time).
C A
= concentration gradient of A in z direction.
z
Note: negative sign refers to drop in concentration, i.e. flux is negative.

For overall passage of solute out of particle and into bulk phase, can use a similar expression,

C A
JA k
z

k depends on diffusivity and variables that control flow such as velocity, viscosity, density
and dimensions.

Integrating concentration of solute A for some distance into the bulk phase, b, gives:

k
JA CS C
b

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 Separation Process Fundamentals H81SPF

CS = concentration at surface
C = concentration in bulk phase at distance b

To obtain rate expression for batch process of volume, V, flux becomes,

C A V C A kA
JA Therefore, CS C
t A t bV

Where A = interfacial surface area

To get concentration profile over time, Integrate for t = 0, C = 0 and t = t, C = C

C
C t kA
bV t
1
C CS
0 CS C 0

which gives,

plotted
t
kA

C C S 1 e bV



t

Fig. 7: Plot of concentration in bulk vs time

The efficiency of an extraction stage is less than 100% for two main reasons. It is impractical
to allow equilibrium to be reached (too much time) and it is impractical to remove all of the
solvent from the solid in the solid/liquid separator (too costly).

Notes:
The solvent which remains with the solid is entrained solvent.
It is often assumed that: Equilibrium has been reached and all solute has been
removed into solvent.
The concentration of solute in the entrained solvent is the
same as in the separated solvent.

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 Separation Process Fundamentals H81SPF

4.0 Single Stage

Consider the following example:

500 kg/hour of an ore, containing 20 wt% copper, is leached in an agitator with a 1000
kg/hour solution of sulphuric acid to extract copper. Assume that all of the copper is
extracted into solution, and perfect mixing is achieved. The slurry is fed to a thickener. If 1
kg of solvent solution per kg of solid ore is entrained, calculate how much copper is extracted
into the overflow solvent solution.

Basis: 1 hour
overflow product agitator/ Solvent
Let C = copper solute
thickener O = inert ore solid
S = sulphuric acid solvent

Feed underflow product

Fig 8: Single leaching stage

In stream 2: In stream 3:

Concentration of C in solvent fed to thickener =

Therefore,
In stream 4:

In stream 1:

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 Separation Process Fundamentals H81SPF

5.0 Multiple Stages (Cascade):

Overall efficiency of a process can be increased by having a number of stages.

Fresh Fresh Fresh

Solvent Solvent Solvent

1 2 3
Feed

Fig. 9: Multiple leaching stages with fresh solvent

The parameters which are either set or need to be determined generally include:

solid feedrate
solid feed composition
amount of solute to be extracted
solvent feedrate
extent of entrainment
No. of stages

Problems are solved by performing material balances.

Consider the following example:

500 kg/hour of an ore, containing 20 wt% copper, is leached in a series of agitators and
thickeners with 1000 kg/hour solutions of sulphuric acid to extract copper. Assume that all of
the copper is extracted into solution, and perfect mixing is achieved. If 1 kg of solvent per kg
of solid ore is entrained in each thickener, calculate the number of agitators required to extract
more than 99 wt% of the copper in the combined overflow solutions.

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 Separation Process Fundamentals H81SPF

Material balances can become complicated for a large number of stages and can be simplified
by creating new parameters.

For example,

mass of solution in overflow

Let R
mass of solution in underflow

If concentration of solute in overflow = concentration of solute in underflow

mass of solute in overflow

R
mass of solute in underflow

With reference to Fig 8 and using S to refer to solute

S1 S 2 S 4
R1
S4 S4

S4 1
Rearranging gives:
S 2 R1 1

For stage 2 and 3

S7 1 S 1
and 10
S 4 R 2 1 S7 R 3 1

and overall,

S10 1 1 1

S2 R1 1 R 2 1 R 3 1

Now, if extent of entrainment is the same for each stage, R1 = R2 = R3, and,

S10 1

S2 R 13

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 Separation Process Fundamentals H81SPF

or more generally,

solute remainingafter n stage 1

st
solute entering1 stage R 1n

6.0 Counter-current Leaching:

In addition to successive leaching stages with fresh solvent, extraction efficiency can be
increased above that achieved using one stage by using a counter-current leaching system.

Solvent
(highest conc.
of solute) Fresh
Solvent

1 n
Feed

Solid
(lowest conc.
of solute)

Fig 10. Counter-current leaching

In stage 1 the solvent with the highest concentration of solute comes into contact with the
untreated solid feed.
In stage n the fresh solvent comes into contact with the solid which has had the most solute
extracted.
System achieves high extractions using less solvent.

In order to simplify the material balances for counter-current leaching systems, the following
parameter is often created.

xn = ratio of solute to solvent solution in stage n.

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 Separation Process Fundamentals H81SPF

Consider the following example:

A slurry containing 100kg of solid CaCO3, 80kg NaOH and 900kg of water is to be washed in
a three stage counter-current arrangement to reduce the amount of NaOH to 1kg. If 3kg of
solution per kg of solid is entrained in each stage, calculate how much water is required.

7.0 Graphical Methods:

Since there are generally three components in a leaching system, i.e. inert solid, solute, and
solvent, the compositions of each component within the various streams in the system can be
represented graphically using a triangular diagram. Drawn on graph paper, these diagrams
can be used to determine the number of stages in a system using a method similar to the
McCabe-Thiele method used for distillation.

Steps for solving counter-current leaching system:

1. Triangle is drawn. (Due to low concentrations in the system, the whole triangle is
sometimes not drawn, just the section needed).
2. Underflow line is drawn. This depends on entrainment.
3. Point for feed is drawn in.
4. Point for overflow composition from 1st stage is calculated through material balance
and drawn in on outer hypotenuse (overflow line).
5. Line (1) is drawn through the feed and 1st overflow points and extended beyond x-
axis.
6. Since the composition of solute in the overflow equals the composition of solute in the
underflow, line (2) is drawn from 1st overflow point to the origin. Where this line
crosses the inner hypotenuse (underflow line) marks the composition of solute and
solvent in the underflow from the 1st stage.
7. The composition in the overflow from the 2nd stage can now be calculated through a
material balance and marked on the overflow line.
8. Line (3) is drawn through the 2nd overflow point and the 1st underflow point and
extended down past the x-axis. Where this line intersects line 1 is the point (see
below). This point allows all other compositions to be determined.

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 Separation Process Fundamentals H81SPF

9. Line (4) is drawn through the origin and 2nd overflow point. Where this line crosses
the underflow line marks the composition of solute and solvent in the underflow from
the 2nd stage.
10. Line (5) is drawn through the point and the 2nd underflow point to the overflow line
to mark the composition of solute and solvent exiting the third stage.
11. Procedure of marking lines through the overflow point and origin to determine the
underflow point and then through the underflow point and the point to determine the
overflow point is repeated until the overflow point reaches that of pure solvent or the
underflow point reaches that in the desired product.

Note: The point or difference point represents the constant difference in flow between
each stage. ie. F2 - F1 = F4 - F3 = F6 - F5 (using stream numbering shown in Fig. 10. F refers
to flowrate.)

The above steps mark out the general procedure for solving counter-current leaching systems.
Procedures will differ depending on what is known and unknown in the system.

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 Separation Process Fundamentals H81SPF

solvent
feed

100%
solvent
composition in
overflow of 2nd stage

composition in
overflow of 1st stage

overflow line

underflow line

100% 100%
solid solute
Feed

composition in
underflow of 1st stage

point

Fig. 11: Graphic presentation of counter-current system.

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