Crystallization

 It is the process by which atoms and molecules arrange themselves into definite
geometrical patterns called crystals.

 Crystallization may be defined also as, a process of formation of solid crystals

from a solution, melt or more rarely a gas.

 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.

 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 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.

 N.B: Supersaturated Solution: is the one that contains more than the
maximum amount of solute that a solvent can hold at specific
temperature.

 Crystallization is an important operation in the chemical industry , as

method of providing:
1- Crystalline materials in the desired size range,
2- A purification step in the industry.
2- Obtain a chemical compound in a stable, pure, free flowing and
elegant form.
 Crystals could be produced from [gases, liquids, or solids] &
[solution, melt, or more rarely a gas].
1- Gaseous to crystalline State:
rare to occur and without specific pharmaceutical applications, examples
are those of sublimation
1- By cooling a liquid:

 Example is freezing water to form ice.

 It may also be illustrated by melting pure sulfur in a vessel and allowing it to
cool until a crust form over the top.
 Holes should then be punched through the crust on opposite sides of the
vessel and the sulfur that is still molten drained off.
 If the quantity of material melted was quite large and the mass cooled
slowly, the crystals formed on the walls of the vessel, and the under surface
of the crust will be large and distinct.
 The presence of impurities retards the crystallization and gives rise to poorly
developed and indistinct crystals.
2- From a Solution: The methods most frequently employed in
the preparation of crystals are :

a) By slowly cooling the solution until the crystals separate

from the solvent.
 The desired substance is first dissolved in a suitable solvent,
filtered, and evaporated to the proper degree, the latter part of
the operation being the most important in determining the size
and perfection of the crystals.
 The solution on cooling should reach the saturation point at a
temperature slightly above room temperature. Crystallization
starts slowly at the saturation point with the evolution of heat,
which is described as an exothermal action.
 The containing vessel and solution which are at a temperature
slightly above that of the room slowly lose heat to the
surrounding air and crystallization proceeds fast enough to
make up for this loss of heat.
 The rate of crystal growth can thus be controlled by properly
insulating the container.
 As a rule, substances which are very soluble in water and
which make concentrated solutions produce small, ill-
defined crystals, while substances which are less soluble
and which make diluted solutions, even when they are
supersaturated, produce crystals with more perfect form.

➢ Perfect rest for a solution designed for crystallization must

be secured if well-defined crystals are desired, and the
solution must not be cooled quickly.

 Sometimes crystals creep or travel up the sides of a

crystallizing vessel, and even over its edge if a small
amount of mother liquor has been allowed to remain.
 If a smooth glass rod having a single scratch upon it, placed in a
solution ready to crystallize, crystals will first attach themselves to
the scratched part, and the smooth part of the rod will not have any
separate crystals upon it.

 It is for this reason, rough stoneware vessels are frequently used for
crystallization.

 Rough surfaces, by offering more points of adhesion, attract the

nuclei upon which the crystalline body is subsequently deposited.

 Sometime crystallizing liquids are seeded or inoculated, by adding

some small perfect crystals from a previous operation, these act as
nuclei for the more rapid formation of crystals.
B- By evaporation of the solvent:
 This process is especially useful where the liquid is more
volatile than water, as alcohol, ether, petroleum benzene, and
chloroform.

 There are some instances in manufacturing pharmacy where

the method is used, but in the case of volatile liquids the
expense attending their loss, if spontaneously evaporated, is
great.

C- By loss of dissolved gases:

 Some of the calcium salts found in hard water are held in
solution in the form of Ca (HCO3)2 calcium bicarbonate.
 On boiling the water the carbon dioxide in solution is driven
off and the bicarbonate converted to the insoluble carbonate,
which is precipitated in a finely crystalline powder.
d) By Chemical Action:
 By this method crystals are commonly formed
through the interaction of two solution to form a new
substance which separates out as a precipitate.
 Reactions may take place between gas and a solution
(hydrogen sulfide and solutions of metals) or between
a solid and a solution (metallic iron and cupric sulfate
solution precipitating metallic copper).

e) By electrolytic deposition:
 This method is commonly known as electroplating
and the deposited metal consists of extremely small
crystals. If the process is carried on slowly with
feeble currents, large crystals may be grown.
➢ Not all the solids behaves the same in the process of crystallization, there is a
lot of conditions and structure characteristics that affect the process.

➢ Also, some solids during the process of crystallization exhibit some changes
that is a characteristic features.

Allotropic changes:
 When sulfur crystals are formed by cooling a liquid and the liquid is poured
off, the interior of the vessel will be found to be lined with long transparent
needles of monoclinic sulfur.

 When these crystals cool below 96oC they become opaque due to the change of
the sulfur to the orthorhombic form.

 The opacity of the crystals is caused by the development of many minute

orthorhombic sulfur crystals, which now occupy the space formerly filled by
the transparent monoclinic needles.

 This transition of monoclinic sulfur to orthorhombic sulfur is called allotropic

changes.
 Many substances exist in two or more crystalline forms and are said to
be polymorphic,

 Polymorphism is the ability of the substance to present in more than

one crystalline structure having the same chemical structure but they
differ in the physical characters such as the melting point, solubility,
.......etc.

 The differences between polymorphic forms is due to differences in

crystalline structure which give rise to differences in physical
properties.

 e.g., The two official varieties of sulfur are different forms of the same
substances.

 If this variety of polymorphism exhibited by elements it is termed

allotropy.
 Many chemical substances of similar chemical
constitution form crystals of similar shape, and are said
to be Isomorphous (the same shape).

 e.g., Magnesium sulphate (MgSO4.7H2O) and Zinc

sulphate (ZnSO4.7H2O).
Amorphous and Crystalline Substances:

 An amorphous substance is one in which the atoms or molecules are

distributed in a random manner throughout the solid.

 On the other hand, a crystalline substance has definite geometrical

internal arrangement of the atoms and molecules.

Crystals and Crystal Structure:

 Crystals are ordinarily defined as solids bounded by natural plane

surfaces called crystal faces. Since the positions and relationship of
the crystal faces to one another of a given substances are definite.

 It is evident that such characteristic phenomena must be due to a

regular interval structure, which is called crystal structure.
 Many substances during the process of crystallizing combine with water and
the water so combined is termed water of crystallization or water of hydration.

 This combination with water must be carefully distinguished from the

mechanical retention of a liquid in the interstices of crystals, which takes place
particularly where the crystals are large and have been formed rapidly.

 Water retained in this way is termed interstitial water, or water of decrepitation,

as it is the cause of the decrepitation of bodies when exposed to heat.
(Decrepitation: The crackling sound made when crystals are heated).

 The sudden expansion of the water causes the substances to crackle and burst
into fragments.

 Crystals containing water of crystallization frequently lose part of it on

exposure to the atmosphere and the transparency noticed when the crystal was
fresh is replaced by opacity and is finally followed by the crumbling and
disintegration of the crystals. This change is termed efflorescence.
 The operation of driving off the water and reducing the
crystals to the form of a dry powder is called exsiccation.

 Some substances absorb water from the atmosphere and

instead of becoming dry, grow moist and in some cases
are converted entirely into liquids. Such substances are
said to be hygroscopic, and the phenomenon is termed
deliquescence. Potassium acetate or zinc chloride, which
has been exposed to moist air, is a familiar example.

 Salts containing water of crystallization are frequently

termed hydrated. Example, monohydrated sodium
carbonate.
The properties of a crystallized substance are controlled
by two factors:
1-The properties of the elements entering into the substance.
Sometimes these are revealed to the elements themselves and
sometimes to molecules or radicals, which enter into the
pattern of the crystals as a molecular unit.

2-The pattern by which the elements are arranged also controls

the properties of the substances.

 Returning again to the example of sulfur crystals, monoclinic

sulfur has a specific gravity of 1.96 and melts at 119.25 oC
while the orthorhombic sulfur has a specific gravity of 2.06
and melts at 112.8oC.
 This term defines the process of crystallizing a substance,
which is comparatively insoluble in simple solvents by
causing it to dissolve in a hot solution of another
substance such as NaCl solution.

 Red mercuric iodide may be made to crystallize in this

way in brilliant scarlet crystals by dissolving it in a hot
solution of sodium chloride, potassium iodide, or mercuric
nitrate.
 Used for the purification of crystalline substances.

 When a fluid containing several component cools, not all the component can
form crystals at the same temperature.

 Ex. The crystallization of hyoscyamine from the mixed alkaloids of belladonna.

 The mixed alkaloids consist mainly of hyoscyamine, hyoscine and

belladonnine.

 The mixture is heated with a suitable quantity of carbon tetrachloride until no

more dissolves; the hot solution is rapidly filtered to remove undissolved
resinous alkaloid (belladonnine) and set aside to crystallize.

 Hyoscyamine crystallizes out of the solution and hyoscine remains dissolved in

the mother liquor.

 The crystals of hyoscyamine are collected and washed with a little carbon
tetrachloride to remove adhering mother liquor.
 The size of crystals usually depends upon the conditions of crystallization.

1- Very small crystals are obtained by the rapid cooling, with frequent stirring,
of solution almost saturated at their boiling point.
 Generally the production of very small crystals of a substance is to be
avoided, because they tend to cohere into masses which are difficult to
wash, and consequently the substance may be less pure than when obtained
in crystals of medium size.

2- Medium-sized crystals are obtained, when crystallizing from water a

saturated solutions at about 60 to 80o C. The hot solution is allowed to cool
slowly and without mechanical disturbance in warm room,

3- Very large crystals are obtained by setting aside a large volume of a

solution and allowing it to evaporate spontaneously.
 The liquid should have been rendered perfectly clear by filtration and the
access of dust must be guarded against.
 The formation of large crystals may be facilitated by "seeding", that is
suspending a well-formed crystal of the solute in the solution, the crystal
acting as a nucleus.
 It is the tendency of the particles of the crystalline materials to
bind together forming solid lumps varying from loose
aggregates to hard solids (cake).

Reasons:
1- A small amount of dissolution taking place at the surface of
the crystals and subsequent re-evaporation of the solvent.
2- Non uniformity of the crystals especially with very small size
crystals.

Prevention:
1- Forming crystals of relatively large and uniform sizes.
2- Addition of small amounts of insoluble materials, such as
stearic acid or a stearate, to adsorb moisture.
1- The curve AB is the ordinary solubility
curve (Equilibrium curve).
2- If a sample of material having the
composition and temperature of point
C is cooled ( Supersaturation by
cooling ) in the direction shown, it first
crosses the solubility curve.
3- If one starts with pure solution, carefully
freed from all solid particles, the
solution will not begin to crystallize until
it has super cooled considerably past
the curve AB
4- Somewhere in the neighbor hood of
point D. Crystallization begins and the
concentration of the substance follow
the curve DE.
5- In the absence of any solid
particles the curve FG (Super-
solubility curve) represents the
limit at which nucleus formation
begins spontaneously, and
consequently the point
crystallization can start D.
6- A solution at L is metastable and
will remains at this point, unless
seed crystals are added, then it
will drop to M on the solubility
curve AB.
7- Any solution above the curve FG
, such as that at N will crystallize
spontaneously on the solubility
curve.
 Crystallizer may be batch or continuous in operation
 continuous crystallizers can be divided into the linear and stirred types.
 Other classification according to the method by which super-saturation is
achieved
A- Cooling B- Evaporative (Calandaria &oslo) C- Vacuum crystallizer
A- Cooling crystallizer:
super saturation results from lowering the temperature of the solution, and this may
achieved by:
1- Atmospheric cooling by natural convection e.g.,
a- Wulff-Bock crystallizer
b- Tank crystallizer
2- Cooling by liquid cooling medium., absorbing heat through metal surface e.g.,
a- swenson-Walker crystallizer
b- Oslo cooler crystallizer
c- Double pipe crystallizer
d- Howard crystallizer
 The main feature of the crystallizer is the method by which the size of the
product is regulated, and this is almost entirely dependent on the control of
Crystallizers

With steam
Evaporative coils
crystallizer With steam
jacket
batch
Cooling With cooling
crystallizer coils
Crystallizers With cooling
jacket
linear type
continuous
Stirred type

 The simplest and cheapest type
 consists of an open tank , which can be used either as an evaporative or as a cooling
crystallizer.
 In the evaporative case, it is generally heated by means of steam coils or from a jacket.
 In the cooling case,
-the solvent is evaporated until the concentration has reached the required
value
- and cooling is then effected by transfer of sensible heat to the surroundings
- The solution cools slowly >>>>> large crystal
>>>>> uneven crystal because the nucleation is not controlled
 The tank is normally rigid to facilitate removal of the mother liquor,but drainage still incomplete.
 Labor costs are high for this type of plant.
 Advantages
- Capacity of the simple tank crystallizer can be increased
-uniformity of the product improved by using an agitator and a series of cooling coils.
 Disadvantage
-crystals form on the surface of the coils >>>>> impede the heat transfer
to overcome this problem : brush the surfaces free of crystals
use Stainless steel construction because particles do not
adhere so firmly as the other materials
.
 They are generally calandria type evaporators with relatively short wide
tubes.
 * The solution is concentrated through calendria.
** then withdrawn to separate the crystals from the mother liquor,
*** mother liquor is then returned to the evaporator together with the feed,
**** evaporator is continued until the concentration of impurities in the
solution becomes excessive.
 evaporators may be operated either at atmospheric or at reduced pressure
( reduced pressures are essential for the formation of many hydrated
crystals).
1- Calandria Evaporator:
 It consists of a very large number of tubes with steam on the outside and the
liquid inside >>>In order to get sufficient heating surface.
 to increase its capacity :
- the tubes are multiplied forming a calandria
- the tubes are lengthened as in the climbing-
film type of evaporator.
 In the crystallizer, the solution is first passed through a heater
 then to flash evaporator before being returned to the crystallizer.
 This type can be operated under reduced pressures for the production of
hydrated crystals, and multiple-effect evaporation is sometimes used..
 Crystallizers employing evaporative cooling crystallization
 often operate under vacuum (low pressure )
 the hot feed is introduced into the body, which generally consists of a
tall vertical cylinder; a low pressure is maintained by means of a steam jet
ejector.
 Flash evaporation of the solution takes place and produces rapid
cooling accompanied by a small increase in concentration.
 The suspension of crystals is then pumped out, either continuously or
in batches.
 In many cases the solution is agitated or continuously circulated by an
external pump in order to prevent stratification ‫تكوين طبقات‬
 the vapour is compressed before it enters the condenser Because
these plants operate at very low pressures, cooling water is not generally
available at a low enough temperature to condense the vapour, and size of
the vapour - condenser is thereby reduced in addition.
 It is a linear type
 consists of a long open trough and divided into a number of sections, each of which
can be independently cooled with water in an external jacket, so that it is possible to
control the rate of cooling throughout.
 A spiral scraper keeps the cooling surfaces free of crystals.

 Sometimes small seed crystals are added to form the nuclei, but more often
spontaneous nucleation is effected in the first section by suitable adjustment of the
temperature.
 Slow cooling is obtained in subsequent sections, and the solution may be cooled below
atmospheric temperature by using refrigerated brines in the jacket.
 This crystallizer is suitable only where supersaturation can be effected by cooling
alone. It gives fairly uniform crystals but some breakage is caused by the scraper
Advantages:
 High capacity
 Uniform crystals
Disadvantages:
 Breakdown of crystals

Due to scraper
Uses: for sugar cryst.
 The Wulff-Bock crystallizer has similar characteristics to the Swenson-
Walker but relies on air-cooling and gives more uniform crystals.

 It consists of
-a trough, mounted on rollers which is slowly rocked from side to side;
-transverse baffles fitted alternately to opposite sides, prevent
surging.
*Because there are no moving parts so it is easily fabricated from
corrosion-resistant materials, and sometimes it is rubber lined.
 It is a linear type cooler crystallizer in which
- the transfer medium flows through an annular jacket
-and the liquid undergoing treatment passes through the narrow space
between the heat transfer surface and the shaft of the mutator, which
carries scraper blades.
 By virtue of the high degree of turbulence and the continuous scraping of the
surface, >>>>>very high heat transfer coefficients are obtained.
 It is extensively used for
- highly viscous or heat-sensitive liquids.
- crystallizing paraffin wax in the petroleum industry
- the plasticizing of margarine and cooking fats.
 It is used where large quantities of crystals of controlled size are
required.
 the basic principle is to induce a supersaturated solution in one part of
crystallizer and released in another.

 A uniform temperature is thereby attained, and the crystals segregate

in the bed with the small ones at the top and the large ones at the bottom
a) Feed rate: Increasing the feed rate causes the material to remain in the
crystallizer for a shorter time, producing small crystals.
b) Feed temp.: Increasing the feed temperature produce a greater
throughout and more concentrated feed.
c) Heat removed in cooler: Increasing the heat removed in the cooler
result in a greater yield and smaller crystals because there is a higher
degree of supersaturation.
d) The circulation rate:
If the rate is too high, supersaturated liquid will enter the pump.
If it is too low, all the supersaturation will be lost before the solution has
reached the top of the crystal bed, and the upper portions of the bed
will be ineffective.
e) The rate of removal of nuclei. The fewer the nuclei present, the larger
will be the final crystals
 It is a cooling crystallizer, cooled
with cold water circulating in a jacket.
 This crystallizer, consists essentially
of a vertical conical device through
which solution flows in an upward
direction. The upper end of the
crystallizer is the wide part of the
cone.
 , Feed solution is introduced from
the bottomand also the product of
crystals is removed from the bottom.
 It is a continuous stirred apparatus,
nucleation starts at definite points, the
crystals grow through circulation and
settle by gravity when become big
enough.
 The size of crystals can be
controlled by regulating the
flow of feed and the
withdrawal of the product.
 Extraction
 Definition: Operation in which a constituent of a solid or of
a liquid is transferred to another liquid (the solvent).
 Types :
1. "solid-liquid extraction“ (solid phase is present)
2. “liquid-liquid extraction" (two liquids)
Examples:
1. Extraction of fixed oils from seeds (alternative to
mechanical expression)
2. Preparation of alkaloids, such as strychnine from Nux
Vomica beans or quinine from Cinchona bark.
3. Isolation of enzymes, such as rennin, and hormones,
such as insulin, from animal sources.
 1- solid liquid extraction

 Also called "leaching", "lixiviation", and "washing".

 Extraction always involves 2 steps :

1. contact of the solvent with the solid to be treated

so as to transfer the soluble constituent (solute) to
the solvent.

2. Separation or washing of the solution from the

residual solid.
 Leaching is always operated as a batch process in
pharmaceutical industries because high cost materials
are processed in relatively small quantities.

 continuous extraction which characterized by large

throughput and counter current pattern of flow Is not
applicable

 Frequent changes of material may be made, creating

problems of cleaning and contamination

 Types (Methods) of Leaching:

1. Leaching by percolation.
2. Leaching by immersion.
Methods of leaching(types)
 1- leaching by percolation,
❖ the raw material is placed in a vessel, forming a permeable
bed through which the solvent or (menstruum) percolates.
❖ Dissolution of the wanted constituents occurs and the
solution issues from the bottom of the bed.

❖ This liquid is sometimes called the miscella .

❖ exhausted solids is called the marc.

 2- leaching by immersion ,
consists of immersing the solid in the solvent and stirring.
After a suitable period of time, solid and liquid are separated.
 Leaching by percolation
(Simple (batch) percolator )
This may be jacketed to give control of
the extraction temperature
1- Coarse ground material is placed
into the body of the extractor

2-The body of the extractor may be

completely filled with the solvent.

3- Liquid is then withdrawn from the

body through the false bottom and
more solvent is added. This is
continued until the marc is
exhausted. (till miscella is free from
wanted constituents)
 
 Sometimes, the solution issuing from the bottom
may be returned to the top. After a period of
recirculation, the liquid is completely withdrawn
and fresh solvent admitted.
 In both processes, a period of steeping or
soaking may precede the movement of liquid.

 In beds of high permeability, adequate

movement of liquid is obtained by simple gravity
operation in an open vessel
 If the material forms a dense bed , the liquid
must be pumped through if suitable flow rates are
to be secured. A closed extraction vessel must
be then used.
.
 Closed extraction vessels are also necessary for
high temperature extraction and extraction with
volatile solvents.

 Sometimes, migration of fine material downwards

lead to formation of a region of low permeability at the
bottom of the bed .This can be prevented by forcing
the liquid upwards through the bed.

 In other processes, the bed may not be immersed in

the menstruum. This is simply sprinkled on to the
upper surface and allowed to trickle (slowly moved)
through the bed, the voids of which are mainly filled
with air.
 Advantages:
1. Simple method for extraction.
2. Solvent recovery - by draining from permeable bed
-or by mechanical expression.

 Disadvantages:
1. Require large amounts of solvent and yield dilute
extracts.
Solution: extraction is followed by evaporation.

Since most materials encountered are heat sensitive,

this will be operated at reduced pressure. The vapor
leaving the evaporator is condensed and returned to the
extractor.
2. Channeling :the liquid flows preferentially,
bypassing other parts of the bed. The bypassed
portions do not get extracted completely.
 Solution: The packing must be even (channeling
is prevented or reduced by horizontal, perforated
plates placed at intervals in the bed. These
redistribute the percolating liquid(.

3. Swelling : Solvent imbibitions will swell dried

materials and the permeability of the bed will be
reduced. This is most marked with aqueous
solvents.
 Solution : it is necessary to moisten the material
with water or with the solvent before it is packed into
the extractor .
 Leaching by immersion
 Leaching by immersion is carried out in simple tanks
which may be agitated by a turbine or paddle.

 If the solids are adequately suspended, intimate

contact between the phases promotes efficient
extraction.
 Incomplete extraction due to channeling is avoided
and difficulties due to swelling do not arise.

 The materials leached by immersion are either finely

divided or coarse and compressible.

 When agitation ceases, the solids will settle and

the leach liquid can be pumped off by lines suitably
placed in the tank.
 Bollman Extractor
(continuous moving bed extractor)
 The Bollman(Hansa Miihle soybean extractor) consists of a

series of large perforated baskets suspended on a pair of

endless chains which are driven by sprockets wheels.
 One of the very oldest continuous extractor and still listed among
the best Extractor.
 The Bollman was invented by H. Bollman in Germany in 1920.
 Bollman Extractor is mainly used for the recovery of additional oil
from the residues obtained after mechanical pressing of solids.
Bollman Extractor
 Bollman Extractor

 When a basket reaches the top of the unit on the

ascending side it is automatically inverted and the

extracted flakes are dumped into the discharge
hopper from which they are taken to driers by the
screw conveyors.

 The entire apparatus is enclosed in a vapor-tight

housing to prevent leakage of the solvent vapors.

 The choice of extraction method

 The choice of extraction method depends primarily

on the physical properties of the basic material and
its particle size.

1. If this material is coarse, rigid powder will form

beds of high permeability >>>> percolation can
be adopted.

2. fine powders or compressible animal tissues, will

not form permeable beds >>>
- the alternative method must be adopted.
 -use of pressure
 The choice of solvent
 Ideal solvent is:

1- cheap, non-toxic and non-inflammable.

2-highly selective(dissolving only the wanted constituents of

the solid(.

3- has a low viscosity (allowing easy movement through

a bed of solids)

4- high vapor pressure (if the resulting solution is to be

concentrated by evaporation)
These factors limit the number of solvents of commercial value.
 Water and alcohol, and mixtures of the two, are
widely used. )Both, however, are non-selective,
leaching varying proportions of gums, mucilages and
other unwanted components.(

 petroleum solvents and benzene and related solvents.

are more selective.

 In many cases, specific properties of the wanted

constituents may suggest a particular solvent.
Ex: Eugenol, can be readily extracted from cloves with
a solution of potassium hydroxide
 Factors affecting the rate of leaching

1- The size and size distribution of the solid

particles.

2- The temperature of leaching.

3- The physical properties of solvent .

4- The relative movement imposed upon the solids

and the liquid.
1- The size and size distribution of the solid particles

 the size reduction by comminution increases the rate of

leaching (comminution):
1- ↓ p.s →  S.A →  rate of leaching

2- cell rupture (  contact, dissolution & diffusion).

But also causes removal of cell wall that prevents movement
of unwanted materials of high m.wt .

3 - ↓ void space → ↓ permeability of bed → ↓ flow rate of solvent

- So optimum p.s should be reached after grinding to 
porosity.
- Removal of fines is a must (fines fill voids between large
particles)
- So narrow distribution of particles sizes is beneficial also in
even packing of bed that prevents channeling.
2- Temperature :
  Temp. of extraction →  solubility of most materials.
  Temp →  diffusion & mass transfer →  rate of
extraction.
 but also temp. should be controlled to avoid:
A- Decomposition of active constituents.
B- inhibition of enzymatic activity.
3 - The physical properties of the solvent:
 The relative properties of the solvent are low viscosity and
free solution of wanted constituents.

4 - The relative movement imposed upon the solids and

the liquid: (Agitation):
 Agitation facilitates diffusion of solute to the bulk of solution
 Agitation keeps fine particles in suspension and facilitates
solvent penetration.
 Liquid-Liquid Extraction

 Operation in which a material dissolved in a liquid is

transferred to another immisible liquid (solvent).

 The solvent must be insoluble in the solution to be

extracted.
 Steps of Liquid-Liquid extraction:

1- Contact (mixing) of the solvent with the solution to be treated

transfer the solute from the solution to the solvent.

2- Separation of the liquid solution phase from the liquid solvent

phase.

3- Recovery of the solvent from each phase.

 The separation and recovery of the solvent :

carried out by various methods such as
- Distillation,
- Simple heating or Cooling: to diminish the solubility of
solute or solvent.
 Uses of liquid-liquid Extraction:

 used for the separation of the components of a solution,

particularly when these components :

1- are relatively nonvolatile .

2- have the same volatilities from the mixture.

3- are sensitive to the temperatures required for the

separation by distillation.

4- are less-volatile and present in the solution only in

relatively small amounts. ( extraction into a second solvent,
producing a more conc. solution economically).
A quantity of feed liquid may be mixed with a quantity of solvent
in an agitated vessel, after which the layers are settled and
separated.

A quantity
a quantity of feed
of solvent liquid

layers are settled and

separated.
 Equipment
 The "extract" layer:
The layer containing greater concentration of the solvent
and smaller concentration of the feed liquid.
 The "raffinate" layer:
The layer containing greater concentration of feed liquid and
smaller concentration of solvent .

 The extract may be lighter or heavier than the raffinate

so the extract may be entered from the top of the equipment
in some cases OR from the bottom in others.

 All extraction equipment attempts to secure a large contact

area between the phases.
 Equipment
❖ The term "wetted-wall" tower is often used for the
vertical type.
❖ In both the horizontal and vertical type of equipment the
extended contact area is obtained by having the
equipment of sufficient length

Different types of contacting columns include:

1- baffle-plate column,
2- spray column,
3- packed column,
4- perforated plate or sieve plate column
5- scheibel column.
➢ All of which are relatively cheap in initial cost and require
little maintenance, and some may have mechanical agitator
.
 5-
5- Scheibel Column
Scheibel Column
 One of the difficulties in using perforated plate or packed columns is
that redispersion of the liquids after each stage is very poor.

To overcome this scheibel

column contains a series of agitators
mounted on a central
rotating shaft. Between
the agitators a wire mesh is fitted that
breaks up any emulsions,
so used for easily emulsified liquid.
 Characteristics of Scheible Column

 Reasonable capacity

 High efficiency due to internal baffling

 Good turndown capability

 Best suited when many stages are required

 Not recommended for highly fouling systems

WITH BEST WISHES