Leaching

Unit - 4
Leaching is a unit operation in which a solid mixture is contacted with a liquid solvent for the
removal of one or more soluble constituent of the solid mixture. It is also called as solid-
liquid extraction or simply solid extraction. It is one of the oldest operations in chemical
industries which involve the use of solvent to remove a solute from a solid mixture.

Lixiviation is used less frequently as a synonym for leaching, although originally it referred
specifically to the leaching of alkali from wood ashes. Decoction refers specifically to the use
of the solvent at its boiling temperature. When the solute material is largely present on the
surface of an insoluble solid and is merely washed off by the solvent, the operation is
sometimes called elutriation or elution.

Contacting a solid mixture with a suitable solvent provides a solution of soluble constituents
in a solvent. It may be used for the production of concentrated solution of a valuable material
or in order to free an insoluble solid from a soluble material with which it is contaminated.
In case of leaching operation, the constituent of solid mixture that dissolves in a given solvent
is called solute and the one which has no solubility in a given solvent is called an insoluble
matter or insoluble solid.

In such operation, the solution (containing soluble constituents and solvent) obtained is called
the overflow/ strong leach solution. The wet solid comprising of insoluble material and
solution associated with it is called as the underflow/ leached solids.

The amount of solution adhering to the solid generally depends upon the time provided for
setting. The solution obtained is generally free of insoluble solid material. The solution may
contain some amount of insoluble material if (i) solid does not settle to give clear solution
and (ii) too much of a solution is withdrawn so that a small amount of solid material are
carried away.

Applications: The metallurgical industries are the largest users of the leaching operation.
Most useful minerals occur in mixtures with large proportions of undesirable constituents,
and leaching of the valuable material is a separation method which is frequently applied. For
example, copper minerals are preferentially dissolved from certain of their ores by leaching
with sulfuric acid or ammonical solutions.

Examples of leaching operation are

(i) Extraction of gold from its ore by using sodium cyanide solution
(ii) Extraction of oil from oil seeds such as a Soya beans using hexane or petroleum
ether.
(iii) Extraction of sugar from sugar beets using hot water
(iv) Extraction of tannin from tea tree bark using water
(v) Extraction of medicinal compounds from the plant roots, leaves and stems
 (vi) Extraction of perfumes from flowers
(vii) Preparation of tea and coffee

Factors affecting the rate of leaching

(1) Particle size: Smaller sized particles provide greater interfacial area between the solid
and liquid which in turn results in higher rate of transfer of material. But the particle
size should not be too small, otherwise the separation of solid part from liquid and
drainage of solid residue will become more difficult.

(2) Solvent: The solvent used should be selective. It should have high soluble capacity
and low viscosity to circulate freely.
(3) Temperature: Generally, the solubility of soluble solute material increases with
increasing temperature, so high temperatures favour the leaching operation. For
example, more tannin will be recovered out of barks by using hot water than cold
water. Considering other factors there should be certain upper limit to the temperature
in case of natural products, high temperature results in chemical deterioration of
product.
(4) Agitation: Agitation increases the eddy diffusion and thus increases the rate of
transfer of material from the solid surface of the bulk of a solution i.e agitation
favours the leaching process. Agitation also prevents the sedimentation/sitting of
solids, keeps the solid particles suspended in liquid and thus helps to make effective
use of the interfacial surface.

Preparation of the solids

The success of a leaching and the technique to be used will very frequently depend upon any
prior treatment which may be given the solid.

In some instances, small particles of the soluble material are completely surrounded by a
matrix of insoluble matter. The solvent must then diffuse into the mass, and the resulting
solution must diffuse out, before a separation can result. This is the situation with many
metallurgical materials. Crushing and grinding of such solids will greatly accelerate the
leaching action, since then the soluble portions are made more accessible to the solvent.

A certain copper ore, for example, can be leached effectively by sulfuric acid solutions within
4 to 8 h if ground to pass through a 60-mesh screen, in 5 days if crushed to 6-mm granules,
and only in 4 to 6 years if l50-mm lumps are used. Since grinding is expensive, the quality of
the ore will have much to do with the choice of size to be leached. For certain gold ores, on
the other hand, the tiny metallic particles are scattered throughout a matrix of quartzite which
is so impervious to the leaching solvent that it is essential to grind the rock to pass through a
IOO-mesh screen if leaching is to occur at all. When the soluble substance is more or less
uniformly distributed throughout the solid or even in solid solution, the leaching action may
provide channels for the passage of fresh solvent and fine grinding may not be necessary.

Vegetable and animal bodies are cellular in structure, and the natural products to be leached
from these materials are usually found inside the cells. If the cell walls remain intact upon
exposure to a suitable solvent, the leaching action involves osmotic passage of the solute
through the cell walls. This may be slow, but it is impractical and sometimes undesirable to
grind the material small enough to release the contents of individual cells. Thus, sugar beets
are cut into thin, wedge-shaped slices called cosseltes before leaching in order to reduce the
time required for the solvent water to reach the individual plant cells.

For many pharmaceutical products recovered from plant roots, stems, and leaves, the plant
material is frequently dried before treatment, and this does much toward rupturing the cell
walls and releasing the solute for direct action by the solvent. Vegetable seeds and beans,
such as soybeans, are usually rolled or flaked to give particles in the size range 0.15 to 5 mm.

When the solute is adsorbed upon the surface of solid particles or merely dissolved in
adhering solution, no grinding or crushing is necessary and the particles can be washed
directly

Steps involved in separation:

The separation of soluble constituents from the solid by means of a solvent i.e leaching
consists of two steps;

(i) Contacting the solid with the selective solvent in order to dissolve soluble solute in
the solvent
(ii) Separation of insoluble phases i.e. the separation of liquid phase and from the solid
phase physically by settling, filtration etc.

The two steps may be carried out in separate equipment or in the same piece of equipment. In
actual practice, it is not possible to separate completely the liquid phase from the solid so the
solid will always retain some amount of solution. In normal operation, the streams leaving the
second step are;

(a) Liquid phase - clear solution of the solute in solvent called overflow
(b) Slurry consisting of solid and adhering solution called underflow

The above-mentioned two steps - contacting solid with the solvent and the separation of over
flow from the underflow constitute one stage and the ideal or equilibrium stage is the one
in which the solution retained by the solid in the under flow is of the same composition
as a clear solution obtained as overflow (y* = x)

In case of leaching, we are generally concerned with the problems of calculation of amount of
soluble solute leached from the solid knowing initial solute content of the solid, amount of
leaching solvent, etc and determination of number of stages required to reduce the solute
content of the solid to some specified value knowing the amount of the solvent, etc.

We will be adopting the graphical procedure for the determination of number of stages and
for the graphical solution will make use of rectangular coordinates
Methods of Operation and Equipment
Leaching operations are carried out under batch and semi-batch (unsteady-state) as well as
under completely continuous (steady-state) conditions. In each category, both stage-wise and
continuous-contact types of equipment are to be found.
Two major handling techniques are used:
 Spraying or trickling the liquid over the solid, and
 Immersing the solid completely in the liquid.

The choice of equipment to be used in any case depends greatly upon the physical form of the
solids and the difficulties and cost of handling them.

UNSTEADY-STATE OPERATION

The unsteady-state operations include those where the solids and liquids are contacted in
purely batch-wise fashion and also those where a batch of the solid is contacted with a
continuously flowing stream of the liquid (semi batch method).

In-Place (in Situ) Leaching:

In-situ leaching (ISL), also called in-situ recovery (ISR) or solution mining, is
a mining process used to recover minerals such as copper and uranium through boreholes
drilled into a deposit, in situ. In situ leach works by artificially dissolving minerals occurring
naturally in a solid state for recovery of material occurring naturally in solution.
The process initially involves the drilling of holes into the ore deposit. Explosive or hydraulic
fracturing may be used to create open pathways in the deposit for solution to penetrate.
Leaching solution is pumped into the deposit where it makes contact with the ore. The
solution bearing the dissolved ore content is then pumped to the surface and processed. This
process allows the extraction of metals and salts from an ore body without the need for
conventional mining involving drill-and-blast, open-cut or underground mining.

Fig. 4.1 In-situ leaching

Heap Leaching:

Low grade ores can be easily leached by this technique where the ores is gathered as a heap
upon impervious ground. The leach liquor is collected over the ore which percolates through
the heap and collected as it drains from the heap. This technique is used for the extraction of
copper and uranium from their low-grade ores.

Fig. 4.2 Heap leaching

Percolation tanks

Whenever small tanks are to be used, they can be made of metal or wood. The solid particles
to be leached, rest on a false bottom which could be made of wood strips and may be covered
by a coconut matting and a tightly stretched canvas filter cloth.

A very large percolation tanks are made of reinforced concrete and lined with the lead or
bituminous mastic.

Small tanks may be provided with the side doors near the bottom for removing the leached
solid while the large tanks are emptied by excavating from the top.

It is always preferable to fill the tanks with particles of uniform size so that voids will be
more and the pressure drop required for the flow of leaching liquid is least. This also leads to
uniform leaching of individual particles.

For these operations the crushed solids may be filled in the tank initially and then the solvent
is allowed to enter in.

The solid and the solvent may retain in contact with each other for a specified amount of time
and then drained.

During the process, if necessary, the liquid can also be circulated through the bed. The liquid
can also be allowed to enter in continuously and also drained continuously.

The liquid from the exit can also be recirculated, if necessary. The flow of liquid could either
be downwards or upwards with proper distribution of liquid.
 Fig. 4.3 Percolation Tank

Shanks System

At times, one is interested in getting a strong solution, which can be obtained by a counter
current operation. This arrangement, also called shanks system, contains number of tanks as
shown in figure.

The number of tanks generally vary from 6 to 16. in a typical system with 8 tanks at
particular time, tank 8 is empty and tank 1 to 7 contain solids.

Fresh solvent enters tank 1, where the solid has spent maximum amount of time and the
material in tank 2, 3, 4, 5, 6 and 7 have progressively spent less time.

The material in 7th tank has spent the least amount of time. The solution withdrawn from the
7th tank has the maximum solute concentration because the solution comes after contact with
fresh solids.

The solution withdrawn from tank 1 goes to tank 2, from tank 2 to tank 3…., from tank 6 to
tank 7.

The leached solid is discarded from tank 1 and fresh solid is now added in tank 8.
The solution is transferred from tank 7 to tank 8, 6 to 7, 5 to 6, …, 2 to 3.

Here the fresh solvent is added in tank 2, and the solid from tank 2 is finally discarded. The
solution now obtained from tank “8” will have maximum solute concentration.

Tank 1 which is now empty will be loaded with a fresh batch of solids. This is nothing but
advancing the tanks by one.
The operation is continued in this manner by keeping successive tanks as the first tank in
which the fresh solvent enters. The solids move counter currently to liquid flow.

Fig. 4.4 Shanks system

Agitated Vessels

These are either vertical or horizontal closed cylindrical vessels with power driven paddles or
stirrers on vertical or horizontal shafts.

They have a provision at the bottom for the withdrawal of leach solution at the end of the
operation. In some of the designs, the horizontal drum is the extraction vessel, and the solid
and liquid are tumbled about inside by rotation of the drum on rollers. They are operated on
batch basis and each one is a single leaching stage.

They can also be used in series for a multistage operation.

For the leaching of finely divided solids, Pachuca tanks is used. This finds extensive use in
metallurgical industries. These tanks are constructed with wood, metal or concrete and lined
with suitable material depending on the nature of the leaching liquid.

Agitation is accompanied by air lift. The bubbles rising through the central tube cause the
upward flow of liquid and suspended solid in the tube and hence circulation of the mixture.
Conventional mechanical agitators are also used for this purpose. Once the desired leaching is
achieved, the agitation is stopped, the solids are allowed to settle and the clear supernatant
liquid is decanted by siphoning over the top of the tank or by withdrawal through discharge
pipe placed at appropriate level in the side of the tank.
Percolation Vs Agitation

If a solid is in the form of big lumps, the question that arises is whether one should go in for
percolation technique or agitation-settling technique. The problem is quite complicated due to
the diverse leaching characteristics of the various solids and the value of solute. However, the
following points are worth considering.

Though fine grinding is more costly and provides more rapid and possibly more through
leaching, the quantity of liquid associated with the settled solid is very large. Hence, one may
have to use large quantity of solvent to recover as much solute as possible. The composited
extract thus obtained could be dilute. Coarsely ground particles, on the other hand, leach
more slowly and possibly less thoroughly and may retain lesser quantity of solution. They
may also require lesser washing and hence the extract could be a concentrated one due to the
use of lesser quantity of solvent.

Practical results have shown that leaching in an agitated vessel is more effective than by
percolation for a fibrous solid like cane.

Hence, one may have to decide based on the economy and the case of operation.

Steady state operations

They are classified as stage wise or continuous contact operations.
Stagewise equipment are sometimes assembled in multiple units to produce multistage
effects, where is continuous contact equipment provide the equivalent of many stages in a
single unit. Some of the solids may also require grinding in order to make the soluble
portions accessible to the leaching solvents. In fact, weight grinding is an operation during
which some leaching could be completed. For example, 50 to 75% of the soluble gold may
dissolved by grinding the ore in the presence of cyanide solution. Castor oil is also extracted
suitably in an attrition mill with solvent.

Agitated vessels

Finely ground solids which can be readily suspended in liquids by agitation can be handled in
agitated vessels. These must be arranged for continuous flow of both liquid and solid in and
out of the tank. Care must be taken to ensure that no accumulation of solid occurs. Due to
thorough mixing, equilibrium is always there between the solid and liquid. HD images
discussed earlier can also be used.

Thickeners

There are mechanical devices which are meant for increasing the ratio of solid to liquid in a
suspension of finely-sized particles by settling and decanting, thus producing a thickened
sludge and a clear supernatant liquid.

They are generally installed before any filter to minimise the filtering cost.

Since both effluents can be pumped and transported, thickeners are frequently used to wash
leached solids and chemical precipitates free of adhering solution in a continuous multistage
counter current arrangement and hence worth their use in leaching operations also.

A typical single-compartment thickener is shown in Fig

The thin slurry of liquid and suspended solids enters a large settling tank through a feed well
at the top centre in such a manner as to avoid mixing the slurry with the clear liquid at the top
of the tank.

The solids settle from the liquid which fills the tank, and the settled sludge is gently directed
toward the discharge cone at the bottom by four sets of plow blades or rakes, revolving
slowly to avoid disturbing the settled solid unduly.

The sludge is pumped from the discharge cone by means of a diaphragm pump.
The clear, supernatant liquid overflows into a launder built about the upper periphery of the
tank.
Continuous counter current decantation

It is an arrangement involving both the thickeners and agitators. The solids enter the first set
of agitators and are mixed with overflow liquid from the 2nd thickener. Then the contents
after through agitation enter the 1st thickener. The agitator along with thickener constituted
the first stage.

The sludge from the first thickener passes on to the 2nd agitator where it is mixed with
overflow from the 3rd thickener and the sludge are then transferred to 3rd agitator where it is
mixed with the overflow liquid from 4th. Fresh solvent enters at last thickener.

Fresh solvents enter the last thickener. The overflow liquid taken out from the first thickener
will have the maximum concentration of solute.

Leaching of vegetable seeds

Leaching of vegetable seeds

Soya beans, cotton seeds, rice bran and castor seeds are some of the products regularly
leached with an organic solvent for removing the oil present in them.

The process involves dehulling, precooking, adjustment of water content and flaking. In some
cases, solvent extraction of oil is preceded by mechanical expression of oil from oilseeds.

Leaching solvents are generally petroleum fractions.

The oil-solvent solution containing small amount of finely divided suspended solids is called
miscella and the solid is called marc.

Rotocel extractor
It is a modification of shanks system where in the leaching tanks are continuously moved
permitting a continuous introduction and discharge of solids it is shown in figure.

It consists of a circular shell partitioned into several cells each fitted with a hinged screen
bottom for supporting the solids.
This shell slowly revolves above a stationary compartmented tank. As the rotor revolves,
each cell passes in turn under the prepared solids feeder and then under a series of sprays by
which the contents of each cell are periodically drenched with solvent for leaching.

By the time one rotation is completed, when the leaching is expected to be completed, the
leached solids of each cell are automatically dumped into one of the lower stationary
compartments, from which they are continuously conveyed away.

The solvent sprayed over each cell filled with solids, percolates downward through the solid
and supporting screen into the appropriate compartment of the lower tank from which it is
pumped to the next spray.

The leaching is counter current, and the strongest solution comes from the cell which is filled
with fresh solid.

It is essential to maintain the equipment properly to ensure smooth operation. It is also

enclosed in a vapour tight housing to prevent the escaping of solvent vapours.

Kennedy extractor

A schematic arrangement is shown in figure. It is a stagewise device, originally used for

leaching tannins from tan bark.

The solids are leached in a series of tubs and are pushed from one to next in a cascade by
perforated paddles, while the solvent flows in counter current direction.

Perforations in paddles permit drainage of liquid from solids between stages, and the solids
are scrapped from each paddle as shown in figure.

The number of tubs depend on the nature of solid, solvent and the level of extraction desired.
Since it has a horizontal orientation, more floor space is required.
Bollman extractor

It has a vertical orientation and has a several perforated baskets attached to a chain conveyor
for conveying solids.

As the chain descends, the solids are leached in parallel flow by a dilute solvent - oils
solution, called half miscella, pumped from the bottom of the vessel and spread over the
baskets at the top.

The liquid percolates through the solids from basket to basket and collects at the bottom as a
final strong solution called full miscella and is withdrawn.

on the ascent, the solids are leached counter currently by a spray of fresh solvent and the
product is called half miscella.

A short drainage time is provided before leached solid in the baskets are pumped at the top. A
schematic diagram is shown in figure.
Continuous horizontal filter

A schematic arrangement of a continuous horizontal filter is shown in figure. The filter in the
form of a circular wheel is divided into a number of sectors and revolves in the horizontal
plane.

Here prepared seeds are slurried with solvent which has already been used for leaching, and
the slurry is sent to the filter.

The first filtrate is passed again through the filter cake to remove finely divided solids before
being discharged as miscella. The principle behind the operation is quite similar to Rotocel
extractor.
Graphical representation of equilibrium conditions in Leaching

A – Pure solvent

B - Insoluble solid

C – Soluble solute

We express the co-ordinates on B-free basis

( )

( )

( )

Types of equilibrium

1st type of equilibrium

This will happen

(i) If enough time of contact with solvent is not

provided
(ii) If adsorption of solute occurs
(iii) If the solute C is soluble in the insoluble solid
B

Figure shows solute C is infinitely soluble in solvent A. Therefore, x and y will have values
over range from 0 to 1. Curve JKL represents underflow compositions. The curve MNP
represents the clear solution withdrawn or overflow compositions. MNP lies above the N = 0
indicates that overflow contains some amount of insoluble solid B. This is due to withdrawn
of solid Bin partially settle solution or the insoluble solid is slightly soluble in solvent.

Here tie-line K-N is not vertical showing that (y > x) C is more in underflow than overflow.

Type II equilibrium

Figure represents a case where adsorption of

solute does not occur, so clear solution
(overflow) is withdrawn.

Solution with underflow have some composition

as overflow (y =x) and tie-lines are vertical.

Line JK represents the underflow composition.

Overflow composition is represented by x-axis
since overflow contains no soluble B.

Type III equilibrium

 The above figure represents a case where solute C has a
limited solubility 𝑥𝑆 in solvent.

Tie-lines before P-S are vertical since no adsorption occurs

and overflow liquid is clear.

After P-S, y >x, since C is increasing in underflow and N is

decreasing [N = B/(A+C) ], the solubility of solute is
limited.

Constant and Variable underflow

Variable underflow: When amount of solution retained by the insoluble solid in the
underflow varies and is a function of solute concentration then we have variable underflow.

The ratio of insoluble to solution (N) in the underflow is not constant and is a function of the
solute concentration value. N Vs y plot is a curve.

Constant underflow: When the amount of the solution retained by the insoluble solid in the
underflow is constant and independent of the solute concentration then we have constant
underflow.
The ratio of the insoluble to the solution in the underflow is constant from all the stages.
N Vs y plot is a straight line.

In the graphical procedure, a plot of N Vs x is represented by x-axis as normally the overflow

contains no insoluble B.
Single Stage Leaching

F – mass (A + C) in solids to be leached

B – mass of insoluble in solids to be leached

( ) in solids to be leached
in solids to be leached

- mass (A+C) in leached solids

B – mass of insoluble in the leached solid

in leached solids

in leached solids
- mass (A+C) in leaching solvent

in leaching solvent

- mass (A+C) in leach solution (overflow)

in leach solution

Consider a single stage leaching operation, in which solids to be leached are contacted with
leaching solvent and the resulting insoluble phases are physically separated as overflow and
underflow.

Since in many cases a clear liquid leach solution (overflow) is obtained i.e the overflow does
not contain any solid B. The insoluble B in the leached solids is the same as that in the solids
before leaching.

Mass of insoluble in leached solid = mass of insoluble in the solids to be leached

Material balance of B
Material balance of solute C

Material balance of solvent A

Material balance of solution (A+C)

Mixing of the solids to be leached and solvent produces mixture

(i) Draw N Vs x, y diagram

(ii) Draw x Vs y diagram
(iii) Locate F ( ) and ( , )
(iv) Join
(v) Locate ( ) on line

(vi) Draw a tie line passing through with the help of equilibrium curve (x Vs
y)
(vii) Read from point

can be estimated
Multistage Cross current leaching

This is simply an extension of single stage leaching in which the leached solids are
successively contacted with fresh leaching solvent.

This may be performed in batch or continuous manner.

Hair leached solids from any stage act as feed to the next, so more and more solute is
removed from the solids as we move along the cascade.

The material balance calculations the are done for single stage are now applicable here to 1st
stage. The calculations for the subsequent stages are to be performed in the same manner,
except that leached solids from any stage act as feed to next stage.

For Stage - 1

Material balance of B

Material balance of solute C

Material balance of solution (A+C)

Mixing of the solids to be leached and solvent produces mixture

For stage -2

For stage -3
 (i) Draw N Vs x, y diagram
(ii) Locate F ( ) and ( , )
(iii) Join
(iv) Locate ( ) on line

(v) Draw a tie line (vertical line) passing through

(vi) Read from point

(vii) Join , Locate ( )

(viii) Draw a tie line (vertical line) passing through

(ix) Repeat the same for stage 3

Problem: 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 of sodium hydroxide, NaOH, 0.125 kg suspended solid/kg
solution. This is settled, the clear sodium 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 lost 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.
 Na2CO3(aq) + Ca(OH)2(s) → 2 NaOH(aq) + CaCO3(s)

Basis: 1 kg solution

Mass of NaOH = 0.1 kg (C)

Mass of water = 0.9 kg (A)
B = 0.125 kg CaCO3 (B)

N = 0.125 kg / kg solution

Original mixture corresponds to M1

 = 0.125 kg / kg solution

Draw graph N Vs y, locate R1 (0.1, 0) and M1 (0.125, 0.1), join R1 and M1 and extend line to
curve to get point E1.

N1 value from graph = 0.47

We know that

Weight of clear solution

Given that equal amount of water is added

Stage -2

is located on the line joining (0, 0)

A tie-line through is drawn. At , = 0.35

Weight of clear solution

Now 0.789 kg of water is added

Stage -3

is located on the line joining (0, 0)

A tie-line through is drawn. At , = 0.012

Weight of clear solution