 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
𝑝𝑎𝑟𝑡𝑠 𝑠𝑜𝑙𝑢𝑡𝑒
100 𝑝𝑎𝑟𝑡𝑠 𝑠𝑜𝑙𝑣𝑒𝑛𝑡
𝑆=
𝑝𝑎𝑟𝑡𝑠 𝑠𝑜𝑙𝑢𝑡𝑒 𝑎𝑡 𝑒𝑞𝑢𝑖𝑙𝑖𝑏𝑟𝑖𝑢𝑚
100 𝑝𝑎𝑟𝑡𝑠 𝑠𝑜𝑙𝑣𝑒𝑛𝑡

 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the crystallizer and is withdrawn as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
XF F = XLL + XCC
 Enthalpy Balance
hFF = hLL + hCC + q
 Heat Balance
qwater = qcrystals
qcrystals = FCpF(tF – tL) + CHC
qwater = WCpH2O (t2 – t1)
 Heat Transfer Equation
q = UADTlm
æ ö

q = UA
( 2) ( L
ç t -t - t -t ÷
ç F 1)÷
ç æ t F - t2 ö ÷
ç ln ç ÷ ÷
è è t L - t1 ø ø
 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 + DL
DP = Ds + DD

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

crystal growth is WS
independent of crystal WP = DS3 ( DS + DD )
3

size, the seed and 3

product masses may be W = W æ DS + DD ö
Sç ÷
related for
P
è DS ø
3
æ DS + éë DP - DS ùû ö
WP = WS ç ÷
è DS ø
3
æ DP ö
WP = WS ç ÷
è DS ø
 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:
 A 20 weight % solution of Na2SO4 at
200°F is pumped continuously to a
vacuum crystallizer from which the
magma is pumped at 60°F. What is the
composition of this magma, and what
percentage of Na2SO4 in the feed is
recovered as Na2SO4·10H2O crystals
after this magma is centrifuged?
 A plant produces 30,000 MT of
anhydrous sulfate annually by
crystallizing sulfate brine at 0°C, yields
of 95% and 90% in the crystallization
and calcinations operations are
obtained respectively. How many
metric tons of liquor are fed to the
crystallizer daily? Note: 300 working
days per year
 1,200 lb of barium nitrate are dissolved
in sufficient water to form a saturated
solution at 90°C. Assuming that 5% of
the weight of the original solution is
lost through evaporation, calculate the
crop of the crystals obtained when
cooled to 20°C. solubility data of
barium nitrate at 90°C = 30.6 lb/100 lb
water; at 20°C = 9.2 lb/100 lb water
 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
XF F = XLL + XCC
 Enthalpy Balance
hFF = hLL + hCC + q
 Heat Balance
qwater = qcrystals
qcrystals = FCpF(tF – tL) + CHC
qwater = WCpH2O (t2 – t1)
 Heat Transfer Equation
q = UADTlm
æ ö

q = UA
( 2) ( L
ç t -t - t -t ÷
ç F 1)÷
ç æ t F - t2 ö ÷
ç ln ç ÷ ÷
è è t L - t1 ø ø
 A Swenson-Walker crystallizer is to be used to
produce 1 ton/h of copperas (FeSO4·7H2O)
crystals. The saturated solution enters the
crystallizer at 120°F. The slurry leaving the
crystallizer will be at 80°F. Cooling water enters
the crystallizer jacket at 60°F and leaves at 70°F.
It may be assumed that the U for the crystallizer
is 35 BTU/h·°F·ft2. There are 3.5 ft2 of cooling
surface per ft of crystallizer length.
 a) Estimate the cooling water required
b) Determine the number of crystallizer
 section to be used.
Data: specific heat of solution = 0.7 BTU/lb·°F;
heat of solution= 4400 cal/gmol copperas;
solubility at 120°F = 140 parts copperas/100
parts excess water; solubility at 80°F = 74 parts
copperas/100 parts excess water
 The solubility of sodium sulfate is 40 parts
Na2SO4 per 100 parts of water at 30°C, and
13.5 parts at 15°C. The latent heat of
crystallization (liberated when crystals
form) is 18,000 g-cal per gmol Na2SO4.
Glauber’s salt (Na2SO4·10H2O) is to be
made in a Swenson- Walker crystallizer by
cooling a solution, saturated at 30°C, to
15°C. Cooling water enters at 10°C and
leaves at 20°C. The over- all heat transfer
coefficient in the crystallizer is 25
BTU/h·ft2·°F and each foot of crystallizer
has 3 sq ft of cooling surface. How many
10-ft units of crystallizer will be required
to produce 1 ton/h of Glauber’s Salt