CHAPTER 3: SOLID – LIQUID

EXTRACTION / LEACHING
 CHAPTER / CONTENT

Introduction to Leaching Process

Rates of Leaching

Types of Equipments for Leaching

Equilibrium Relations in Leaching

Calculation in Leaching
 Introduction to Leaching Process

Widely used in the metallurgical, natural product and food industries

under batch, semi – continuous or continuous condition.

The major difference between Leaching and LLE centers about the difficulty
to transport the solid or the solid slurry from stage to stage.

Leaching or also known as solid – liquid exraction involves dissolving

soluble material from its mixture with an insoluble solid.

Many biological inorganic or biological organic substances occur in a

different mixture of different components in a solid.

In order to separate the desired solute constituent or remove the

undesirable solute component from the solid phase, the solid is contacted with
a liquid phase.
 Introduction to Leaching Process

The two phases are in intimate contact and the solute or solutes can diffuse from
the solid to the liquid phase, which causes a separation of the components
originally in the solid.

This process is called liquid – solid leaching or simply leaching.

Leaching process for biological substances

An important such process is to leach sugar from sugar beets with hot water.

In production of vegetable oils, organic solvents such as hexane, acetone and

ether are used to extract the oil from peanuts, soybeans, flax seeds, castor beans,
sunflower seeds, etc.

In pharmaceutical industry, many different pharmaceutical products are

obtained by leaching plan roots, leaves and stems.

For ‘instant’ coffee, ground roasted coffee is leached with water and soluble tea
is produced by water leaching of tea leaves.

Tannin is removed from tea barks by leaching with water.

 Introduction to Leaching Process

Leaching process for inorganic and organic materials

Used in metal – processing industries

In metal ores, the desired metal components usually occur with a large amount
of undesirable constituents and leaching is used to obtain these metal
components in the form of metal salts.

E.g.: Copper salts are leached by dissolving raw copper ores by using sulfuric
acid or ammoniacal solutions.

E.g.: Nickel salts are leached using sulfuric acid – ammonia – oxygen mixures.

Gold is leached using an aqueous sodium cyanide solution.

 Rates of Leaching

PRINCIPLES OF LEACHING

RATE OF LEACHING WHEN DISSOLVING A SOLID

METHODS OF OPERATING IN LEACHING

 Principles of Leaching

The solvent must be transferred from the bulk solvent solution to the
surface of the solids.

Next, the solvent must penetrate or diffuse into the solids.

The solute then diffuses through the solid solvent mixture to the surface
of the particle.

Finally, the solute is transferred to the bulk solution.

The rate of the solvent transfer from the bulk solution to the solid surface
is quite rapid.

However, the rate of transfer of the solvent into the solid can be rather
slow or rapid.

This solvent transfer usually occurs initially when the particle are first
contacted with the solvent.
 Principles of Leaching

The rate of diffusion of the solute through the solid and solvent to the
surface of the solid is often the controlling resistance in the overall leaching
process and can depend on a number of different factors.

If the solid is made of porous and solid structure with the solute and
solvent in the pores in the solid, the diffusion through the porous solid can
be described by an effective diffusivity.

In biological or natural substances, additional complexity occurs because

of the cell present, in the leaching of thin sugar beet slices, one – fifth of the
cells are ruptured in the slicing of the beets.

The leaching of sugar is then similar to the washing process, where in the
remaining cells, sugar must diffuse out through the cell walls. With
soybeans, whole bean cannot be leached effectively. The rolling and flaking
of the soybeans ruptures cell walls so that the solvent can more easily
penetrate by capillary action.

The resistance to mass transfer to the solute from the solid surface to the
bulk solvent is generally quite small compared to the resistance to the
diffusion within the solid itself.
 Rate of leaching when dissolving a solid

When a material is being dissolved from the solid to the solvent solution,
however, the rate of mass transfer from the solid surface to the liquid is the
controlling factor.

There is essentially no resistance in the solid phase if it is a pure materials.

The equation for this can be derived as follows from a batch system.

The rate of mass transfer of the solute A being dissolved to the solution of
volume V in m3 is:

whe re

NA  kg mol of A dissolving to the solution pe r se cond

 k L c AS  c A   Eq.1
NA A  the surfaceare aof particle s in m 2
A kL  masstansfe rcoe fficie nt in m/s
c AS  saturationsolubility of the solid solute A in the
solution in kg mol/m 3
c A  conce ntration of A in the solution at time t se cin
kg mol/m 3
 Rate of leaching when dissolving a solid

By material balance, the rate of accumulation of A in the solution is equal

to equation (1) times the area:

 N A  Ak L c AS  c A 
dc A
V
dt
Integrating from time t = 0 and cA = cA0 to t = t and cA = cA:
cA t
dc A Ak L
c c AS  c A V
  dt
t 0
A0

c AS  c A
 e k L A V  t
c AS  c A0
The solution approaches a saturated condition exponentially.

Often the interfacial area A will increase during the extraction if the
external surface becomes very irregular.

If the soluble materials forms a high proportion of the total solid,

disintegration of the particles may occur.
 Rate of leaching when dissolving a solid

Example 12.8 – 1. Prediction of Time for Batch Leaching

Particles having an average diameter of approximately 2.0 – mm are

leached in a batch type apparatus with a large volume of solvent.

The concentration of the solute A in the solvent is kept approximately

constant.

A time of 3.11 hour is needed to leach 80% of the available solute from the
solid.

Assuming that diffusion in the solid is controlling and the effective

diffusivity is constant, calculate the time of leaching if the particle size is
reduced to 1.5 mm.
 Rate of leaching when dissolving a solid

Solution 12.8 – 1. Prediction of Time for Batch Leaching

For 80% extraction, the fraction unextracted ES is 0.20.

Using Figure 5.3 – 13 for a sphere, for ES = 0.20, a value of DAeff t/a2 = 0.112
is obtained, where DAeff is the effective diffusivity in mm2/s, t is time in s, and
a is radius in mm.

For the same fraction ES, the value of DAeff t/a2 is constant for a different
size. Hence,
t1a22
t2  2  Eq.3
a1

where t2 is time for leaching with a particle size a2. Substituting in

equation above:

t2  3.11
1.5 2
2
 1.75 h
2.0 22
 Methods of operating in leaching

Can be carried out in batch or unsteady state conditions, continuous and

steady state conditions.

Both continuous and stage wise types of equipment are used in steady or
unsteady state operations.

In steady state leaching a common method used in the mineral industries

is in – place leaching, where the solvent is allowed to percolate through the
actual ore body.

For example, copper is leached by sulfuric acid from sulfides ore by leach
liquor is pumped over a pile of crushed ore and collected at the ground level
as it drains from the heap.
 Types of Equipments for Leaching

FIXED – BED LEACHING

MOVING BED LEACHING

AGITATED SOLID LEACHING

 Fixed – Bed Leaching

Used in beet sugar industry and is also used for extraction of tanning
extracts from the tanbark, extraction of pharmaceuticals from barks and
seeds and other processes.

Figure 12.8-1 shows a typical sugar beet diffuser or extractor.

The cover is removable so that

sugar beet slices called cossettes can
be dumped into the bed.

Heated water at 344 K to 350 K

flows into the bed to leach out the
sugar.

The leached sugar solution flows

out the bottom onto the next tank in
series.

About 95% of the sugar in beets is

leached to yield an outlet solution
from the system of about 12 wt%.
 Moving – Bed Leaching

There are number of devices for stagewise countercurrent leaching where

the bed or stages moves.

Used widely in extracting oil from vegetable seeds such as cottonseeds,

peanuts and soybeans.

The seeds are usually dehulled first, sometimes precooked, often partially
dried and rolled or flaked.

The solvents used are

particularly hydrocarbons such
as hexane and the final solvent
– vegetable solution called
miscella may contain some
finely divided solids.
 Agitated Solid Leaching

When the solid can be ground fine abou 200 mesh (0.074 mm), it can kept
in suspension by small amounts of agitation.

Continuous countercurrent leaching can be accomplished by placing the

number of agitator in series, with setttling tanks or thickeners between each
agitator.

Sometimes thickeners are used as combination contactor – agitators and

settlers – shown in Figure 12.8-3.
 Equilibrium Relations in Leaching

To analyze single – stage and countercurrent – stage leaching, an operating line

equation, or material balance relation and the equilibrium relations between the
two streams are needed as in LLE.

Assumptions made by achieving the equilibrium relations:

Sufficient solvent is present so that all the solute in the entering solid dissolved
in the solvent.

The solute in the entering solid dissolved completely in the first stage.

No adsorption of the solute by the solid.

* This means the solution in the liquid phase leaving a stage is the same as the
solution that remains with the solid matrix in the settled slurry leaving the stage.

The settled solid leaving a stage always contains some liquid in which dissolved
solids is present.

The solid – liquid stream is called underflow or slurry stream.

 Equilibrium Relations in Leaching

Consequently, the concentration of oil or solute in the liquid or overflow stream is

equal to the concentration of solute in the liquid solution accompanying the slurry
or underflow stream.

The amount of solution retained with the solids in the settling portion of each
stage may depend the density and viscosity of liquid in which the solid is
suspended.

Equilibrium diagrams for leaching:

The concentration of inert or insoluble solid B in the solution mixture or the
slurry mixture can be expressed in kg (lbm) units:

kg B kg solid lb solid
N  
kg A  kg C kg solution lb solution

For overflow, N = 0

For underflow, N value depending on the solute concentration in the liquid.

 Equilibrium Relations in Leaching

The composition of solute A in liquid will be expressed as wt fractions:

kg A kg solute
xA   overflowliquid 
kg A  kg C kg solution

kg A kg solute  liquid in slurry or 

yA    
kg A  kg C kg solution  underflow liquid 
 Calculation in Leaching

SINGLE – STAGE LEACHING

COUNTER – CURRENT MULTISTAGE LEACHING

 Single – stage Leaching

Process flow

Overflow solution Solvent Feed

V1, x1 V2, x2

Feed Slurry Underflow solution

L0, N0, y0, B L1, N1, y1, B

V Mass of overflow solution xA Composition of A at overflow solution

L Mass of liquid in slurry solution yA Composition of A at slurry solution
B Mass of dry, solute – free solid.

Material balance is divided into 3 parts:

L0  V2  L1  V1  M Total solution balance

L0 y A0  V2 x A2  L1 y A1  V1 x A1  Mx AM Comp. A balance
B  N 0 L0  0  N1 L1  0  N M M Solid balance
 Single – stage calculations

Example 1

In a single – stage leaching of soybean oil from flaked soybeans with hexane, 100
kg of soybean containing 20 wt% oil is leached with 100 kg of fresh hexane solvent.

The value of N for the slurry underflow is essentially constant at 1.5 kg insoluble
solid/kg solution retained.

Calculate the amounts and compositions of the overflow V1 and the underflow
slurry L1 leaving the stage.
 Single – stage calculations

Solution 1

Overflow solution Solvent Feed

V1, x1 V2, x2

Feed Slurry Underflow solution

L0, N0, y0, B L1, N1, y1, B

Information given:

Feed slurry = 100 kg containing 20 wt% oil

Entering solvent, V2 = 100 kg N = 1.5 kg B/kg (A+C)

 Single – stage calculations

Solution 1

Find coordinate at L0.

Mass of A = 0.20 x 100 A = 20 kg

Mass of B = 0.80 x 100 B = 80 kg

Mass of C = 0 kg C = 0 kg

A A 20
y A0     1.0
L0 A  C 20  0
B B 80
N0     4.0
L0 A  C 20  0

Coordinate for L0 (yA0 , N0) = (1.0 , 4.0)

 Single – stage calculations

Solution 1

Find coordinate at V2.

Mass of A = 0 A = 0 kg

Mass of B = 0 B = 0 kg

Mass of C = 100 kg C = 100 kg

A A 0
x2    0
V2 A  C 0  100
B B 0
N2    0
V2 A  C 0  100

Coordinate for V2 (x2 , N2) = (0 , 0)

 Single – stage calculations

Solution 1

From material balance calculations:

Total solution balance:

L0  V2  L1  V1  M
20  100  M M  120 kg

Component A balance:

L0 y A0  V2 x A2  Mx AM
201.0  1000  120x AM
x AM  0.167
 Single – stage calculations

Solution 1

Solid balance:

B  N 0 L0  N1 L1  N M M
N 0 L0  N M M
420  N M 120 N M  0.667

Coordinate for M (xM , NM) = (0.167 , 0.667)

Plot coordinate M in the graph.

Construct straight vertical line through point M in order to find value V1 and
L1
 Single – stage calculations

Solution 1

4
L0
3.5
3
2.5
N

2 L1 N versus y A
1.5
1
M
0.5
V1 N versus x A
0
0 V2 0.2 0.4 0.6 0.8 1
x A, y A

From figure,

Coordinate for V1 (x1 , N1) = (0.167 , 0)

Coordinate for L1 (y1 , N1) = (0.167 , 1.5)

 Single – stage calculations

Solution 1

From material balance calculations:

Total solution balance:

L1  V1  M
L1  V1  120
V1  120  L1  Eq.1

Solid balance:

B  N 0 L0  N1 L1  N M M
N1 L1  N M M
1.5L1   0.667 120 L1  53.36 kg
 Single – stage calculations

Solution 1

From material balance calculations:

From Eq. (1)

V1  120  L1  Eq.1
V1  120  53.36 V1  66.64 kg
 Multi – stage counter current Leaching

Process flow

Overflow solution Solvent Feed

V1, x1 VN+1, xN+1

Feed Slurry Underflow solution

L0, N0, y0, B LN, NN, yN, B

V Mass of overflow solution xA Composition of A at overflow solution

L Mass of liquid in slurry solution yA Composition of A at slurry solution
B Mass of dry, solute – free solid.
 Multi – stage counter current Leaching

The ideal stages are numbered in the direction of the solids or underflow stream.

The solvent (C) – solute (A) phase or V phase is the liquid phase that overflows
continuously from stage to stage countercurrently to the solid phase, and it
dissolves solute as it moves along.

The slurry phase L composed of inert solid (B) and liquid phase of A and C is the
continuous underflow from each stage.

Composition of V – denoted by x

Composition of L – denoted by y

Assumption: The solid B is insoluble and is not lost in the liquid V phase.

The flow rate of solid is constant throughout the process

Multi – stage counter current Leaching

L0  VN 1  LN  V1  M Total solution balance

L0 y A0  VN 1 x AN 1  LN y AN  V1 x A1  Mx AM Comp. A balance

B  N 0 L0  N N LN  N M M Solid balance
 Multi – stage counter current Leaching

Example 2
A continuous countercurrent multistage system is to be used to leach oil from meal
by benzene solvent (B3).

The process is to treat 2000 kg/h of inert solid meal (B) containing 800 kg oil (A)
and also 50 kg benzene (C).

The inlet flow per hour of fresh solvent mixture contains 1310 kg benzene and 20
kg oil. The leached solids are to contain 120 kg oil.

Data (B3) are tabulated below as N kg inert solid B/kg solution and yA kg oil A/kg
solution

Calculate the amounts and concentrations of the stream leaving the process and the
number of stages required.
 Multi – stage counter current Leaching

Solution 2

Overflow solution Solvent Feed

V1, x1 VN+1, xN+1

Feed Slurry Underflow solution

L0, N0, y0, B LN, NN, yN, B

Information given:

Feed slurry (L0):

A = 800 kg/h B = 2000 kg/h C = 50 kg/h

Entering solvent (VN+1 )

A = 20 kg/h B = 0 kg/h C = 1310 kg/h

 Multi – stage counter current Leaching

Solution 2

Overflow solution Solvent Feed

V1, x1 VN+1, xN+1

Feed Slurry Underflow solution

L0, N0, y0, B LN, NN, yN, B

Information given:

Underflow solution (LN):

A =120 kg/h B = 2000 kg/h C = ?? kg/h

 Multi – stage counter current Leaching

Solution 2

Find coordinate at L0.

Mass of A = 800 kg/h

Mass of B = 2000 kg/h

Mass of C = 50 kg/h

A A 800 800
y A0      0.94
L0 A  C 800  50 850
B B 2000 2000
N0      2.35
L0 A  C 800  50 850

Coordinate for L0 (yA0 , N0) = (0.94 , 2.35)

 Multi – stage counter current Leaching

Solution 2

Find coordinate at VN+1.

Mass of A = 20 kg/h

Mass of B = 0 kg/h

Mass of C = 1310 kg/h

A A 20 20
xN 1      0.015
VN 1 A  C 20  1310 1330
B B 0
N N 1    0
VN 1 A  C 20  1310

Coordinate for VN+1 (xN+1 , NN+1) = (0.015 , 0)

 Multi – stage counter current Leaching

Solution 2

Find coordinate at LN.

Mass of A = 120 kg/h

Mass of B = 2000 kg/h

Mass of C = ?? kg/h
NN
Slope of graph,
yN
B
N N LN B 2000
    16.67  N  16.67 y
yN A A 120
LN

If y = 0.1, N = 16.67 x 0.1 = 1.67

Plot New Coordinate (y , N) = (0.1 , 1.67)

 Multi – stage counter current Leaching

Solution 2

3
LN
2 L0
1
0
VN 1
-0.4 -0.2 -1 0 0.2 0.4 0.6 0.8 1
N

-2
-3
-4
-5
-6
-7
x A, y A
 Multi – stage counter current Leaching

Solution 2

From material balance calculations:

Total solution balance:

L0  VN 1  LN  V1  M
L0  VN 1  M
850  1330  M M  2180 kg

Component A balance:

L0 y A0  VN 1 xN 1  Mx AM
8500.94  13300.015  2180x AM
x AM  0.376
 Multi – stage counter current Leaching

Solution 2

From material balance calculations:

Solid balance:

B  N 0 L0  N N LN  N M M
N 0 L0  N M M
2.35850  N M 2180 N M  0.916

Coordinate for M (xM , NM) = (0.376 , 0.916)

Plot coordinate M in the graph.

Construct line from point LN to point M until it cross at x – axis. Point at x –

axis = V1
 Multi – stage counter current Leaching

3
LN
2 L0
M
1
V1
0 VN 1
-0.4 -0.2 0 0.2 0.4 0.6 0.8 1
-1
N

-2
-3
-4

-5
-6
-7
x A, y A
From figure,

Coordinate for V1 (x1 , N1) = (0.592 , 0)

Coordinate for LN (y1 , N1) = (0.12 , 2.0)

 Multi – stage counter current Leaching

Solution 2

From material balance calculations:

Total solution balance:

V1  2180  LN  Eq.1

Component A balance:
LN y N  V1 x1  Mx AM
LN 0.12   V1 0.592   2180 0.376 

Inse rtEq. 1 into e quationabove

LN 0.12   2180  LN 0.592   2180 0.376 
0.12 LN  1290.56  0.592 LN  819.68
0.472 LN  470.88  LN  997.62 kg
 Multi – stage counter current Leaching

Solution 2

From material balance calculations:

Total solution balance:

V1  2180  LN  Eq.1
V1  2180  997.62

V1  1182.38 kg

Construct operating point:

Connect L0 with V1 & LN with VN+1. The cross line – operating point.

Total stages: 4 stages

 Multi – stage counter current Leaching

Solution 2
Construct the stages:

3
LN L3 L2
2 L1 L0
M
1
V1
0 VN 1
-0.4 -0.2 0 0.2 0.4 0.6 0.8 1
-1
N

-2
-3
-4

-5
P -6
-7
x A, y A