Leaching

◼ Leaching: is the separation of a

solute from solid mixture by
dissolving it in a liquid phase.
◼ Leaching occurs in two steps:
◼ 1. Contacting solvent and solid to effect a transfer of
a solute (leaching).

◼ 2. The separation of the solution from the remaining

solid (washing).
◼ Extraction of a soluble constituent
from a solid by means of a solvent.

◼ e.g.: extraction of sugar from beet

◼ There is only one liquid phase; there

is no distribution equilibrium.
◼ Aim:

◼ - production of a valuable matter in a

concentrated solution or

◼ - to free an insoluble solid from

soluble contamination(e.g.: pigment)
 Leaching Process for Biological
Substances
◼ Leaching of sugar from sugar beets
with hot water.

◼ •Production of vegetable oil, where

organic solvent, e.g. hexane,
acetone and ether, are used to
extract oil from peanuts, soybens,
sunflower seeds, cotton seeds
◼ Pharmaceutical products are
obtained by leaching plant roots,
leaves, and stems.

◼ •Production of soluble instant coffee

where ground roasted coffee is
leached with fresh water.

◼ •Soluble tea is produced by water

leaching of tea leaves.
Leaching Process for Inorganic
and Organic Materials
◼ Extensively used in the metals
processing industries.

◼ •Leaching is used to remove metals

as soluble salt.

◼ •Copper salts are dissolved or

leached from its ore by sulfuric acid
or ammoniacal solutions.
◼ Gold is leached from its ore using
aqueous sodium cyanide solution.

◼ Cobalt and nickel salts are leached

using sulfuric acid-ammonia-oxygen
mixtures
 Preparation of Solid Leaching
◼ Crushing and grinding of solid to
allow soluble portions are made
more accessible to the solvent thus
increasing rate of leaching.

◼ •Simple washing can be applied if

the soluble substance is widely
distributed throughout the whole
solid.
◼ For biological material, i.e. sugar
beet, they are cut into wedge-shape
slices for leaching.

◼ •For soybeans and many vegetable

seeds they are ruptures by rolling
and flaking in such a way that the
vegetable oil is easily accessible to
the solvent.
◼ •For pharmaceutical product e.g.
leaves, stems and roots, drying of
the material before extraction help to
rupture the cell wall and hence
solvent can directly dissolved the
solute.
◼ Factors determining the method of
extraction
◼ - Proportion of the soluble
constituent
◼ - Its distribution throughout the solid
◼ - Nature of the solid (granulator or
cellular)
◼ Particle size (coarse or fine solid) If
the soluble material is in small
isolated packets

◼ in a material impermeable to the

solvent

◼ the solid must be crushed before the

extraction. e.g.: gold dispersed in
rock
◼ Sugar beet has cellular structure.

◼ Cell walls impede the extraction of high

molecular weight contaminations.

◼ Beet is cut in long strips. (The cell walls

are not destroyed.)

◼ Extraction of oil from seeds: The solute is

liquid, it may diffuse towards the solvent
◼ Factors influencing the rate of
extraction
Particle size If it is smaller

• Greater specific surface area (+) :

• Smaller distance within the solid (+)

• Lower settling velocity

◼ Lower settling velocity

❖ separation sol./liq. is more difficult(-)

❖ particles can be maintained in

solution by agitation (+)
◼ Solvent Requirements:

◼ - selectivity

◼ - low viscosity
◼ Temperature

◼ higher Temperature will provide

• highr solubility
• DAB increases
• lower viscosity
◼ Agitation of the fluid

◼ - It increases the turbulence

◼ - It prevents the settling of solid

particles

◼ - It promotes mass transfer

 FACTORS INFLUENCING THE
RATE OF Solid EXTRACTION
The selection of the equipment for an extraction
process is influenced by the factors which are
responsible for limiting the extraction rate.

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.

Solvent:The liquid chosen should be a good

selective solvent and its viscosity should be
sufficiently low for it to circulate freely.
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
◼ 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 particles to tha
bulk of the solution.
 LEACHİNG EQUİPMENT
When the solids form an open ,permeable mass
throughout the leaching operation ,solvent may be
percolated through an unagitated bed of solids.

With impermeable solids or materials that dissintegrate

during leaching,the solids are dispersed into the solvent
and are later separated from it.Both methods may be either
batch or continuous.
Leaching by percolation through
stationary solid beds

Stationary solid-bed leaching is done in a

tank with a perforated false bottom to
support the solids

and permit drainage of the solvent.

Solids are loaded into the tank,sprayed with

solvent until

their solute content is reduced to the

economical minimum,and excavated.
◼ In some cases one passage of solvent through
the material is sufficient ,

◼ but countercurrent flow of solvent through a

battery of tanks is more common.

◼ In this method, fresh solvent is fed to the tank

containing the solid that is most nearly extracted;

◼ it flows through the several tanks in series and is

finally withdrawn from the tank that has been
freshly charged.such a series of tanks is called an
extraction battery.
 Moving-bed leaching

In the machines that are used for this type of

leaching,

the solids are moved through the solvent with little or no

agitation.

The bollman extractor (figure a) contains a bucket

elevator in a closed casing.

There are perforations in the bottom of each Bucket

At the top right-hand corner of the machine ,the

buckets are loaded with flaky solids
◼ such as soybeans and are sprayed with appropriate
amounts

◼ of half miscella as they travel downward.

◼ Half miscella is the intermediate solvent containing some

extracted oil and some small solid particles.

◼ As solids and solvent flow cocurrently down the right-hand

side of the machine

◼ the solvent extracts more oil from beans.

Simultaneously the fine solids are
filtered out of the solvent,

so that clean full miscella can be

pumped from the right –hand sump

at the bottom of the casing.

Bollman extractor
◼ As the partially extracted beans rise through the left side of
the machine ,

◼ a stream of pure solvent percolates countercurrently

through them.

◼ It collects in the left-hand sump and is pumped to the half-

miscella storage tank.

◼ Fully extracted beans are dumped from the buckets at the

top of the elevator into a hopper from which they are
removed by paddle conveyors.
In the Rotocel extractor,illusrated
in figure ,

a horizontal basket is divided into

walled compartments

with a floor that is permeable to

the liquid.

Rotocel extractor
◼ The basket rotates slowly about a vertical axis.

◼ Solids are admitted to each compartment at the feed point;

◼ the compartments then successively pass a number of

solvent sprays,

◼ drainage section, and a discharge point at which the floor of

the compartment opens
◼ to discharge the extracted solids.

◼ The empty compartment moves to the feed to point to

receive its next load of solids.

◼ To give countercurrent extraction, fresh solvent is fed only

to the last compartment before the discharge point,

◼ and the solids in each preceeding compartment are washed

with the effluent from the succeeding one.
 Dispersed –solid leaching

Solids that form impermeable beds,

either before or during leaching ,

are treated by dispersing them in the solvent by mechanical

agitation in a tank or flow mixer.

The leached residue is then separate from the strong solution by

settling or filtration.

Small quantities can be leached batchwise in this way in an

agitated vessel with a bottom drawoff for settled residue.
 Crystallization
Crystallization is the (natural or artificial)
process of formation of solid crystals
precipitating from a solution, melt or more
rarely deposited directly from a gas .
Crystallization is also a chemical solid–liquid
separation technique, in which mass
transfer of a solute from the liquid solution
to a pure solid crystalline phase occurs.
Crystallization is therefore obtained
through a variation of the solubility
conditions of the solute in the solvent
• The crystallization process consists of two
major events, nucleation and crystal growth.
• Nucleation is the step where the solute
molecules dispersed in the solvent start to
gather into clusters, on the nanometer scale
(elevating solute concentration in a small
region), that become stable under the current
operating conditions.
However, when the clusters are not
stable, they redissolve. Therefore,
the clusters need to reach a critical
size in order to become stable nuclei.
Such critical size is dictated by the
operating conditions (temperature,
supersaturation, etc.).
• It is at the stage of nucleation that the
atoms arrange in a defined and periodic
manner that defines the crystal structure —
note that "crystal structure" is a special
term that refers to the relative arrangement
of the atoms, although those are a result of
the internal crystal structure.
 The crystal Growth
The crystal growth is the subsequent growth
of the nuclei that succeed in achieving the
critical cluster size. Nucleation and growth
continue to occur simultaneously while the
supersaturation exists.
◼ Supersaturation is the driving force
of the crystallization,
◼ hence the rate of nucleation and
growth is driven by the existing
supersaturation in the solution.
◼ Once the supersaturation is
exhausted, the solid–liquid system
reaches equilibrium and the
crystallization is complete.
•Artificial methods
For crystallization (recrystallization) to
occur from a solution it must be
supersaturated. This means that the
solution has to contain more solute
entities (molecules or ions) dissolved
than it would contain under the
equilibrium (saturated solution).
◼ This can be achieved by various
methods, with
◼ (1) solution cooling,

◼ (2) addition of a second solvent to

reduce the solubility of the solute
(technique known as anti solvent or
drown-out),
◼ (3) chemical reaction and

◼ (4) change in pH being the most

common methods used in industrial
practice. Other methods, such as
solvent evaporation, can also be
used.
 Purpose of Crystallizer
◼ Used to recover pure solids from
solution

◼ Highly desirable end product

because of:
• Exceptional purity
• Ease of handling
• Long shelf life

◼ One of the final treatment steps in

the purification and concentration of
insulin
 Mechanism of Crystallization
◼ Crystal nucleation and amorphous
precipitates are in competition during
supersaturation conditions

◼ Nucleation favored by slowly exceeding

the equilibrium point of saturation
• permits time for the protein structure
to orient in a crystalline lattice
 Continuous or Batch Design
◼ Benefits of Continuous
• Can maintain solution in supersaturated state
• Large fluidized bed for crystallization
• Minimizes operation costs
• Minimize down time (startup and shutdown)

◼ Benefits of Batch
• Good when have low concentration of product,
high viscosity or many impurities
• Can produce high quality crystal
 Methods of Crystallization
◼ Supersaturation: liquid (solvent)
contains more dissolved solids (solute)
than can ordinarily be accommodated at
that temperature

◼ Can be achieved by several methods:

• Cooling
• Evaporation
• Solvent addition
• Precipitant Addition
 Cooling Method
◼ Concentrated
solution gradually
cooled below
saturation
temperature (50-
60°C) to generate a
supersaturated state
◼ Yields well defined
micron-sized crystals
◼ Shell and tube heat
exchanger is used to
cool solution
 Cooling Method
◼ Advantages:
• High purity downstream
◼ Disadvantages:
• Temperature change does not always have a
positive effect on supersaturation in proteins
• Protein stability may be at risk
• Solubility can be relatively insensitive to
temperature at high salt concentrations
• Cooling will only help reach supersaturation in
systems where solubility and temperature are
directly related
 Evaporation Method
◼ Solute dissolves in solution when heated
to a certain temperature (75°C)
◼ Slowly cooled until crystals precipitate
◼ Shell and tube heat exchanger is used to
heat and cool solution
 Evaporation Method
◼ Advantages:
• high purity levels downstream
◼ Disadvantages:
• Vaporization chamber requires high
pressures
• Protein viability very sensitive to high
temperatures
 Solvent Method
◼ Solvents are generally good protein
precipitants
◼ Their low dielectric constants lower the
solvating power of their aqueous
solutions
◼ Requires acidic solvent
• For crystallization, an insulin protein falls
out of solution at isoelectric point
pH 5.4-5.7
 Solvent Method
◼ Advantages:
• Proteins viability not at risk due to
temperature change
◼ Disadvantages:
• Possible protein contamination due to
insufficient downstream solvent
recovery
 Addition of Zinc Ions
◼ In the presence of zinc ions, insulin
proteins orient to form hexamer
structures

◼ Zinc ions render insulin insoluble which

results in micro-crystallization and
precipitation

Human Insulin Hexamer with Zinc ion

 Seeding Techniques
◼ Primary nucleation is the first step in
crystallization - growth of a new
crystal
• Can bypass primary nucleation (creation
of new crystals) by "seeding" the
solution

◼ Secondary nucleation is crystal

growth initiated by contact
• Accelerated by "seeding" adding existing
insulin crystals to perpetuate crystal
 Crystal Size and Growth Rate
◼ Crystal size distribution is important for the
production process; affects:
• downstream processing
• solids transport
• caking and storage properties of the material
◼ Correct crystal size vital for economic production
◼ Crystals produced in commercial crystallization
processes are usually small
• 30 to 100 um in diameter