§ Refers to solid – liquid separation

§ Solid particles are formed within a homogenous

phase
§ It can occur as:
§ 1. Formation of solid particles in a vapor
§ 2. Formation of solid particles from a liquid
melt
§ 3. Formation of solid crystals from a solution
§ The process usually involves two steps:

§ 1. Concentration of solution and cooling of

solution until the solute concentration
becomes greater than its solubility at that
temperature
§ 2. Solute comes out of the solution in the form
of pure crystals
§ Crystal – highly organized type of
matter, constituent particle - orderly
arranged & repetitive manner
§ Arranged – three dimensional arrays –
SPACE LATTICES
§ - measure of the quantity of the solids
actually present in solution as
compared to the quantity that is in
equilibrium with the solution
#$%&' '()*&+
100 #$%&' '().+/&
!=
#$%&' '()*&+ $& +0*1)12%1*3
100 #$%&' '().+/&

§ Cannot occur without supersaturation.

§ 1. Evaporation – evaporating a portion
of the solvent
§ 2. Cooling – cooling a solution through
indirect heat exchange
§ 3. Vacuum Cooling – flashing of feed
solution adiabatically to a lower
temperature and inducing
crystallization – simultaneous cooling
and evaporation of the solvent
§ 4. Reaction – chemical reaction with a
third substance
§ 5. Salting – addition of a third
component to change the solubility
relationship
§ Two basic steps in over-all process of
crystallization from supersaturated
solution
§ 1.) Nucleation
§ A. Homogenous or Primary Nucleation –
occurs due to rapid local fluctuations on a
molecular scale in a homogenous phase
§ B. Heterogenous Nucleation – occurs in
the presence of surfaces other than
those of the crystals such as surfaces of
walls of the pipe or container, impellers
in mixing or foreign particles
§ C. Secondary Nucleation – occurs due
to the presence of crystals of the
crystallizing species
§2.) Crystal Growth – a layer –
by – layer process
§A. Solute diffusion to the
suspension-crystal interface
§B. Surface reaction for absorbing
solute into the crystal lattice.
§ 1. Yield
§ 2. Purity of Crystals
§ 3. Size of the Crystals
§ 4. Shapes of the Crystals
§ Two-phase mixture of mother liquor
and crystals of all sizes, which occupies
the crystallizer and is withdrawn as
product
§ (1) Cubic system – 3 equal axes at right angles
to each other
§ (2) Tetragonal – 3 axes at right angles to each
other, one axis longer than the other 2
§ (3) Orthorhombic – 3 axes at right angles to
each other, all of different lengths
§ (4) Hexagonal – 3 equal axes in one plane at
60° to each other, and a fourth axis at a right
angle to this plane and not necessarily at the
same length
§ (5) Monoclinic – 3 unequal axes two at
right angles in a plane, and a third at
some angle to this plane
§ (6) Triclinic – 3 unequal axes at unequal
angles to each and not 30°, 60°, or 90°
§ (7) Trigonal -3 unequal and equally
inclined axes
§ (1) May be classified according to
whether they are batch or continuous in
operation
§ (2) May be classified according on the
methods used to bring about
supersaturation
§ (3) Can also be classified according on
the method of suspending the growing
product crystals
§ Either tables or curves
§ Represent equilibrium conditions
§ Plotted data of solubilities versus
temperature
§ In general, solubility is dependent
mainly on temperature although
sometimes on size of materials and
pressure
§ Parts by mass of anhydrous materials
per 100 parts by mass of total solvent
§ Mass percent of anhydrous materials or
solute which ignores water of
crystallization
§Crystallizers that obtain
precipitation by cooling a
concentrated hot solution;
applicable for substance that have
solubility curve that decreases
with temperature
§Batch operation;
§Seldom used in modern practice,
except in small scale operations;
§Usually give a low quality product
§ Consist of an agitated tank;
§ Usually cone-bottomed, containing
cooling coils
§ Simplicity of operation and flexibility
§ A continuous crystallizer consist of an
open round bottomed-trough,
§ 24-in wide by 10 ft long
§ Containing a long ribbon mixer that
turns at about 7 rpm.
§ Crystallizers that obtain precipitation
by evaporating a solution
§ Applicable for the substance whose
solubility curve is flat that yield of
solids by cooling is negligible
§ Acceptable to any substance whose
solubility curve is not to steep
§ The most common of the evaporating
crystallizers;
§ In older form, the crystallizer consisted
of an evaporator below which were
settling chambers into which the salt
settled
§ Modern form of evaporating crystallizer;
§ this unit is particularly well adopted to the
production of large-sized uniform crystals
that are usually rounded;
§ it consists essentially of a forced circulation
evaporator with an external heater
containing a combination of salt filter and
particle size classifier on the bottom of the
evaporator body
§ Where:
§ F = mass of the feed solution
§ L = mass of the mother liquor

§ C = mass of the crystals

§ W = mass of the cooling water

§ XF = mass solute (salt) in the feed solution per mass of feed in

solution
§ XL = mass of solute (salt) in the mother liquor per mass of
mother liquor
§ XC = mass of solute (salt) in the crystals per mass of crystals
§ Where:
§ hF = enthalpy of the feed solution
§ hL = enthalpy of the mother liquor

§ hC = enthalpy of the crystals

§ qwater = heat absorbed by the cooling water

§ qcrystals = heat loss by the crystals

§ CpF = specific heat of the feed solution
§ CpH2O = specific heat of cooling water

§ HC = heat of crystallization
§ Where:
§U = overall heat transfer coefficient
§ A = heat transfer area
§ tF = temperature of the feed solution
§ tL = temperature of the mother liquor
§ t1 = inlet temperature of cooling water
§ t2 = outlet temperature of cooling water
§ Over – all Material Balance
F=L+C
§ Solute Balance
X F F = X L L + XC C
§ Enthalpy Balance
hF F = hL L + hC C + q
§ Heat Balance
qwater = qcrystals
qcrystals = FCpF(tF – tL) + CHC
qwater = WCpH2O (t2 – t1)
§ Heat Transfer Equation
q = UAΔTlm
⎛ ⎞

q = UA
( 2) ( L
⎜ t −t − t −t ⎟
⎜ F 1)⎟
⎜ ⎛ t F − t2 ⎞ ⎟
⎜ ln ⎜ ⎟ ⎟
⎝ ⎝ t L − t1 ⎠ ⎠
§ Over – all Material Balance
F = L + C +V
§ Solute Balance
XF F = XLL + XCC
§ Solvent Balance
(1-XF )F = V + (1- XL)L + (1-XC) C
§ Enthalpy Balance
hFF = hvV + hLL + hCC
§ Heat Balance
qwater = qcrystals
qcrystals = FCpF(tF – tL) + CHC
qwater = WCpH2O (t2 – t1)
§ Where:
§ F = mass of the feed solution
§ L = mass of the mother liquor
§ C = mass of the crystals
§ W = mass of the cooling water
§ V = mass of the evaporated solvent
§ XF = mass solute (salt) in the feed solution per mass of feed in
solution
§ XL = mass of solute (salt) in the mother liquor per mass of
mother liquor
§ XC = mass of solute (salt) in the crystals per mass of crystals
§ Where:
§ hF = enthalpy of the feed solution
§ hL = enthalpy of the mother liquor

§ hC = enthalpy of the crystals

§ hV = enthalpy of the vapor

§ HC = heat of crystallization
§ qwater = heat absorbed by the cooling water
§ qcrystals = heat loss by the crystals

§ CpF = specific heat of the feed solution

§ CpH2O = specific heat of cooling water
§ Where:
§ tF = temperature of the feed solution
§ tL = temperature of the mother liquor
§ t1 = inlet temperature of cooling water
§ t2 = outlet temperature of cooling water
§ΔL Law of Crystals
§ States that if all crystals in magma grow in a
supersaturation field and at the same
temperature and if all crystal grow from birth
at a rate governed by the supersaturation,
then all crystals are not only invariant but
also have the same growth rate that is
independent of size
§ The relation between seed and product particle sizes may be
written as
LP = Ls + ΔL
DP = Ds + ΔD

§ Where:
§ LP or DP = characteristic particle dimension of the product
§ LS or DS = characteristic particle dimension of the seed
§ ΔL or ΔD = change in size of crystals and is constant
throughout the range of size present
 WP = a ρ D = a ρ ( DS + ΔD )
3 3
§ Since the rate of linear P

crystal growth is WS
3( S )
3

independent of crystal WP
= D + ΔD
DS
size, the seed and 3
product masses may be W = W ⎛ DS + ΔD ⎞
S⎜ ⎟
related for P
⎝ DS ⎠
3
⎛ DS + ⎡⎣ DP − DS ⎤⎦ ⎞
WP = WS ⎜ ⎟
⎝ DS ⎠
3
⎛ DP ⎞
WP = WS ⎜ ⎟
⎝ DS ⎠
§ All the crystals in the seed
have been assumed to be of
the same shape, and the
shape has been assumed to
be unchanged by the growth
process.
§ Through assumption is
reasonably closed to the
actual conditions in most
cases.
§ For differential parts of the
crystal masses, each
consisting of crystals of
identical dimensions: