CHE 0313

HEAT AND
MASS TRANSFER
CRYSTALLIZATION
1

Engr. Peniel Jean A. Gildo, MS ChE

Chemical Engineering Department
Pamantasan ng Lungsod ng Maynila
 CRYSTALLIZATION
 a solid-fluid separation process where the solid
particles are formed from a homogeneous phase.
 a simultaneous heat and mass transfer operation in
which mass transfer of solute from the homogeneous
phase to a pure crystalline phase occurs.
Crystallization can occur as:
1. formation of solid particles from a vapor phase (snow
particles)
2. formation of solid particles from a liquid melt
3. formation of solid particles from a liquid solution – the
most important commercially
Crystallization is also an important separation process
that purifies fluids by forming solids.
 CRYSTALLIZATION
The process usually involved two steps:

1. Concentration of solution and

cooling of solution until the
soluble concentration becomes
greater than its solubility at
that temperature.

2. Solute comes out of the

solution in the form of pure
crystals.
 CRYSTALLIZATION
Crystal
 it is a highly organized type of matter
 can be defined as a solid composed of atoms, ions or
molecules which are arranged in an orderly and
repetitive manner.
 the particles are arranged in orderly three-
dimensional arrays called space lattices.
 CRYSTALLIZATION
Some Industrially Important Particulate
Crystals
Ceramic
Bulk Chemicals Catalysts
Precursors
Electronic
Detergents Dyestuffs
Materials
Fiber
Fertilizers Fine Chemicals
Intermediates
Foodstuffs Mineral Ores Pharmaceuticals
Specialty
Polymers Proteins
Chemicals
 CRYSTAL GEOMETRY
 The ideal solid crystal comprises a rigid lattice of ions,
atoms or molecules, the location of which are
characteristic of the substance.
 The regularity of the internal structure of this solid
body results in the crystal having a characteristic
shape; smooth surfaces or faces develop as crystal
grows, and planes of these faces are parallel to atomic
planes in the lattice.

 A particular feature of crystals is that the angles

between two corresponding faces of a given substance
are constant reflecting their internal lattice structure.
 CRYSTAL GEOMETRY
 X-ray Diffraction measures the interatomic distances
between these imaginary planes in a crystal as are the
angles between these planes.

 Crystals are classified on the basis of the interfacial

angles.
 TYPES OF CRYSTAL GEOMETRY
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 two.
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 right angle to this
plane 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
other and not 30°, 60°, nor 90°.
7. Trigonal – 3 unequal and equally inclined axes.
TYPES OF CRYSTAL GEOMETRY
 EQUILIBRIUM SOLUBILITY
 Equilibrium is attained when the solution or the
mother liquor is saturated.
 The saturated solution is represented by the line in a
solubility curve.
 Solubility – the maximum amount of solute that can
be dissolved in a given amount of a solvent at a given
temperature.

 Solubility is usually dependent on temperature while

practically independent of pressure.
EQUILIBRIUM SOLUBILITY

Solubility Curves of Some

Salts in Water
EQUILIBRIUM SOLUBILITY

Solubility of Sodium Thiosulfate,

Na2S2O3, in water
 EQUILIBRIUM SOLUBILITY
 Supersaturation – a measure of the quantity of
solids actually present in the solution compared to the
quantity that is in equilibrium with the solution.

parts solute
100 parts solvent
S
parts solute at equilibrium
100 parts solvent
 For crystallization to occur, supersaturation must be
present.
 METHOD OF GENERATING
SUPERSATURATION
1. Evaporation – by evaporating a portion of the
solvent.
2. Cooling – by cooling a solution through indirect
heat exchange.
3. Vacuum Cooling – by flashing the feed solution
adiabatically to a lower temperature and inducing
crystallization by simultaneous cooling and heating
of the solvent.
4. Reaction – by chemical reaction with a third
substance.
5. Salting – by the addition of a third component to
change the solubility relationship.
MECHANISMS OF CRYSTALLIZATION
Nucleation:
1. Homogeneous or Primary Nucleation
 As a result of rapid and random fluctuations of
molecules in a homogeneous solution, the molecules
may come together and associate into a cluster.
 The loose aggregates may quickly disappear
because of dissolution.
 If the supersaturation is high enough, enough
particles may associate to form a nucleus and grow.
 This is important for operations where there is high
supersaturation and no agitation.
MECHANISMS OF CRYSTALLIZATION
Nucleation:
2. Contact Nucleation
 Heterogeneous Nucleation – the formation of
new nuclei is due to the interference of the
contacting agent (walls of the container or agitator
blades) with clusters of solute molecules becoming
organized growing crystals or actual breakage of
microscopic growths on the surface of the growing
crystals.
 Secondary Nucleation – the formation of new
nuclei occurs in collisions between crystals.

The intensity of agitation is important in contact

nucleation.
MECHANISMS OF CRYSTALLIZATION
Crystal Growth:
 a layer-by-layer process
 the subsequent growth of the nuclei that succeed in
achieving the critical cluster size
 solute diffuses through the suspension–crystal
interface
 Surface reaction for absorbing solute into the
crystal lattice

Nucleation and Growth continue to occur

simultaneously while supersaturation exists.
MECHANISMS OF CRYSTALLIZATION
ΔL Law of Crystal Growth:
 McCabe showed that all crystals are geometrically
similar and of the same material in the same
solution grow at the same rate.

 Growth is measured as the increase in length, ΔL,

in mm, in linear dimension of one crystal.

 The increase is for corresponding distances on all

crystals and is independent of the initial size of the
crystal, provided that the crystals are subject to the
same environmental conditions.
MECHANISMS OF CRYSTALLIZATION
ΔL Law of Crystal Growth:
 Mathematically:
L
G
t
Δt is time in h and growth rate G is a constant in
mm/h.
D1 is the linear dimension of a given crystal at time t1
and D2 at time t2.

L  D2  D1  G  t2  t1 

 The total growth, ΔL is the same for all crystals.

MECHANISMS OF CRYSTALLIZATION
MECHANISMS OF CRYSTALLIZATION
Solubility and Crystal Size
 In comparison, a crystal with a smaller size has a
larger surface energy per unit mass; thus, a smaller
crystal has a greater solubility than the larger one.
 The data on solubility usually applies to moderately
large crystals; thus, in a supersaturated solution, a
small crystal can be in equilibrium.

 If small- and large-sized crystals are present, the

larger crystals will grow and the small crystal will
be dissolved – Oswald ripening.
EQUIPMENT FOR CRYSTALLIZATION
Classifications of Crystallizers:
1. Batch or Continuous
2. Methods used to bring about supersaturation.
 Cooling the solution with negligible evaporation
(i.e. tank and batch-type crystallizers)
 Evaporation of solvent with little to no cooling
(i.e. evaporator–crystallizers and crystallizing
evaporators)
 Combined cooling and evaporation in an adiabatic
evaporator (i.e. vacuum crystallizers)
3. Method of suspending the growing product crystals
 agitated, circulated in a heat exchanger, or
circulated in a scraped surface exchanger
EQUIPMENT FOR CRYSTALLIZATION

Tank Crystallizer
EQUIPMENT FOR CRYSTALLIZATION

Scraped Surface Crystallizers

EQUIPMENT FOR CRYSTALLIZATION
Scraped Surface Crystallizers

Swenson-Walker Crystallizer
EQUIPMENT FOR CRYSTALLIZATION
Circulating–Liquid Evaporator–Crystallizer

Oslo Crystallizer
EQUIPMENT FOR CRYSTALLIZATION
Circulating–Magma Evaporator–Crystallizer
 CRYSTALLIZATION PROCESS
 Solution is concentrated by
Solvent evaporating the solvent
 The concentrated solution is
cooled until the concentration
becomes greater than its
Solution solubility at that temperature

Solvent

Mother
Concentrated Liquor
Solution

Magma
Crystals
 CRYSTALLIZATION PROCESS
Important Factors in a Crystallization Process

 Yield

 Purity of Crystals

 Size of the Crystals – should be uniform to

minimize caking in the package, for ease of
pouring, ease in washing and filtering and for
uniform behavior when in use.
 Shape of the Crystals
 CRYSTALLIZATION PROCESS
Solvent (V)
Mother Liquor
L, xL, TL, hL
Magma (G)
Feed
Crystallizer
F, xF, TF, hF
Cooling Water Crystals
t2 t1 C, xC, TC, hC

 Mother Liquor – the solute-solvent mixture

 Magma – two-phase mixture of mother liquor and
crystals of all sizes which occupies the crystallizer
and is withdrawn as the product
 Anhydrous Crystals – a chemical compound
without water. It is applied particularly to salts
lacking their water of crystallization.
 CRYSTALLIZATION PROCESS
Solvent (V)
Mother Liquor
L, xL, TL, hL
Magma (G)
Feed
Crystallizer
F, xF, TF, hF
Cooling Water Crystals
t2 t1 C, xC, TC, hC

 Hydrates – inorganic salts containing water

molecules combined in a definite ratio as an
integral part of the crystal that are either bound to
a metal center or that have crystallized with the
metal complex.
 Heat of Crystallization – latent heat evolved
when solid forms from a solution; opposite of heat
of solution.
 CALCULATION METHODS
Solvent (V)
Mother Liquor
L, xL, TL, hL
Magma (G)
Feed
Crystallizer
F, xF, TF, hF
Cooling Water Crystals
t2
Material Balances t1 C, xC, TC, hC

Overall Material Balance (OMB)

F V  LC
Solute Balance
x = mass fraction of the solute
xF F  xL L  xC C
Solvent Balance
1  xF  F  1  xL  L  1  xC  C  V
 CALCULATION METHODS
Solvent (V)
Mother Liquor
L, xL, TL, hL
Magma (G)
Feed
Crystallizer
F, xF, TF, hF
Cooling Water Crystals
t2
Enthalpy Balances t1 C, xC, TC, hC

*If Enthalpy Concentration Data are available

F hF  L hL  C hC  V HV  q
Heat Balances
*If the specific heats, heat of solution, and heat of
crystallization are available
q  V V  F CP, F TF  TC   C H C
 CALCULATION METHODS
Solvent (V)
Mother Liquor
L, xL, TL, hL
Magma (G)
Feed
Crystallizer
F, xF, TF, hF
Cooling Water Crystals
t2 t1 C, xC, TC, hC
Heat Removed from Crystallizer
q  m H2OCP,H2O  t2  t1 
Heat Transfer Equations

TLM 
 TF  T2   TL  T1 
q  UATLM  TF  T2 
ln  
 TL  T1 
 METHODS OF SATURATION
Crystallization by Cooling:
Solvent (V)
Mother Liquor
L, xL, TL, hL
Magma (G)
Feed
Crystallizer
F, xF, TF, hF
Cooling Water Crystals
t2 t1 C, xC, TC, hC

 It involves crystallizers that obtain precipitation by

cooling the concentrated solution; applicable for
substance that have solubility curve that decreases
with temperature; for normal solubility curves
which are common for most substances.
 Equipment: Swenson-Walker Crystallizers, Pan
Coolers, Agitated Batch Coolers
 METHODS OF SATURATION
Crystallization by Adiabatic Evaporation
with Cooling:
Solvent (V)
Mother Liquor
L, xL, TL, hL
Magma (G)
Feed
Crystallizer
F, xF, TF, hF

Crystals
C, xC, TC, hC

 Equipment: Vacuum Crystallizers

 METHODS OF SATURATION
Crystallization by Evaporation:
Solvent (V)
Mother Liquor
L, xL, TL, hL
Magma (G)
Feed
Crystallizer
F, xF, TF, hF

External Crystals
Heating
C, xC, TC, hC

 Heat is supplied by an external source.

 Equipment: Oslo Crystallizer

 IMPORTANT SOURCES OF DATA
Solubility Data of Inorganic Salts
 Table 2-122, ChE HB, 8ed
Heats of Solution of Inorganic Salts at 18°C
 Table 2-182, ChE HB, 8ed
Phase Diagrams
 MgSO4-H2O system, Fig. 27.3 (MS, 7ed)
Enthalpy-Concentration Diagrams
 MgSO4-H2O system, Fig. 27.4 (MS, 7ed)
IMPORTANT SOURCES OF DATA

Fig. 27.3 (MS, 7ed): Phase Diagram of MgSO4-H2O system

IMPORTANT SOURCES OF DATA

Fig. 27.4 (MS, 7ed): Enthalpy-

Concentration Diagram of
MgSO4-H2O system
EXAMPLES:
A salt solution weighing 10,000 kg with 30 wt%
Na2CO3 is cooled to 293 K (20°C). The salt
crystallizes as the decahydrate. What will be
the yield of Na2CO3•10H2O crystals if the
solubility is 21.5 kg anhydrous Na2CO3 per 100
kg total water? Do this for the following cases:
a. Assume that no water evaporated.
b. Assume that 3% of the total weight of the
solution is lost by evaporation of water in
cooling.

41
EXAMPLES:
A feed solution of 2268 kg at 327.6 K (54.4°C)
containing 48.2 kg MgSO4 per 100 kg total water is
cooled to 293.2 K (20°C), where MgSO4•7H2O
crystals are removed. The solubility of the salt is
35.5 kg MgSO4 per 100 kg total water. The average
heat capacity of the feed solution can be assumed
to be as 2.93 kJ/kg-K. The heat of solution at 293.2
K (20°C) is –13.31 × 103 kJ/kg-mol heptahydrate.
Calculate the yield of crystals and make a heat
balance to determine the total heat absorbed, q,
assuming that no water is vaporized.

42
EXAMPLES:
A Swenson-Walker crystallizer is to be used to
produce 1 ton per hour of copperas (FeSO4•7H2O)
crystals. The saturated solution enters the
crystallizers at 120°F. The slurry leaving the
crystallizer will be at 80°F. Cooling H2O enters the
crystallizer jacket at 60°F and leaves at 70°F. It
may be assumed that the overall heat transfer
coefficient for the crystallizer is 35 Btu/ft2-hr-°F.
There are 3.5 ft2 of cooling surface per feet of
crystallizer length.
a. Estimate the cooling H2O required.
b. Determine the number of 10-ft 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 43

water; solubility at 80°F = 74 parts copperas/100 parts

excess water
EXAMPLES:
A solution of MgSO4 containing 43 grams of
solid per 100 grams of water is fed to a vacuum
crystallizer at 220°F. The vacuum in the
crystallizer corresponds to a water boiling
temperature of 43°F and a saturated solution of
MgSO4 has a boiling point elevation of 7°F.
How many pounds of Epsom salt
(MgSO4•7H2O) can be produced per hour from a
feed rate of 1 ton/hr? What percentage of
MgSO4 in the feed is recovered as Epsom salt?

44
EXERCISES:
A solution consisting of 30% MgSO4 and 70%
H2O is cooled to 60°F. During cooling, 5% of the
total water in the system evaporates. How
many kilograms of crystals are obtained per
1000 kg of original mixture?

47
EXERCISES:
A 32.5% solution of MgSO4 at 120°F (48.9°C),
without appreciable evaporation, to 70°F (21.1
°C) in a batch water-cooled crystallizer. How
much heat must be removed from the solution
per ton of crystals?

48
EXERCISES:
A feed solution of 10000 lbm at 130°F containing
47.0 lb FeSO4 per 100 lb water is cooled to 80°F,
where FeSO4•7H2O crystals are removed. The
solubility of the salt is 30.5 lb FeSO4 per 100 lb
water. The average heat capacity of the feed
solution is 0.70 BTU/lbm-°F. The heat of solution
at 18°C is –4.4 kcal/gmol FeSO4•7H2O, Calculate
the yield of crystals and make a heat balance.
Assume that no water is vaporized.

49
EXERCISES:
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.

50
EXERCISES:
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.

51
EXERCISES:
What is the yield of sodium acetate crystals (CH3COONa
•3H2O) obtainable from a vacuum crystallizer operating at
1.33 kN/m2 when it is supplied with 0.56 kg/s of a 40%
aqueous solution of the salt at 353 K. The boiling point
elevation of the solution is 11.5 K.
DATA: HC = 144 kJ/kg trihydrate
CP of solution = 3.5 kJ/kg-K

Solubility data:
T (°C) kg/100 kg water
0 36.3
10 40.8
52
20 46.5
30 54.5
 CRYSTALLIZER DESIGN
 The expected particle-size distribution of the
crystals obtained is an important factor in the
design of the crystallization equipment.
 The dried crystals are screened to determine
particle sizes.

 The percent retained on different-sized screens is

recorded.

 The screens or sieves used are the Tyler standard

screens, whose sieve or clear openings in mm are
given in Appendix A.5.3 (G, 4ed)
 CRYSTALLIZER DESIGN
 Mesh size is the mesh number and its relationship
to the size of the openings in the mesh and thus the
size of particles that can pass through these
openings.
 It is defined as the number of
openings in one linear inch of
screen.

 A 4-mesh screen means there

are four little square
openings across one inch of
screen; A 100-mesh screen
has 100 openings per inch,
and so on.
 CRYSTALLIZER DESIGN
Seeding
Solvent
Seed Crystals Mother Liquor
WS, DS

Magma
Feed Crystallizer

Cooling Water Product Crystals

Crystal Mass Balance: WP  WS  C WP, DP

Let: DP ─ characteristic size of product crystals

DS ─ characteristic size of seed crystals
Volume of Particles: V  aD 3
WP DP3
Weight of Products: WP   aD 3  3
P WS DS
Weight of Seeds: WS   aD 3
S
 CRYSTALLIZER DESIGN
ΔL Law of Crystal Growth:
 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:
DP  DS  D
Weight of Products: WP   aDP3
Weight of Seeds: WS   aDS
3
 CRYSTALLIZER DESIGN
ΔL Law of Crystal Growth:
Weight of Products: WP   aD 3
P
WP   a  DS  D 
3

Weight of Seeds: WS   aDS3

3
WP  DS  D 
Ratio:  
WS  DS 
3
 D 
WP  1   WS
 DS 
For differential parts of the crystal masses:
3
WP WS  D 
WP   dWP   1   dWS
0 0
 DS 
EXAMPLES:
A Swenson-Walker crystallizer is fed with
saturated solution of MgSO4 at 110°F. The
solution and its crystalline crop (MgSO4•7H2O)
are cooled to 40°F. The inlet solution contains
1 g of seed per 100 g solution. The seeds are 80
mesh. Assuming ideal growth, what is the
mesh size of crystals leaving the cooled
product? Evaporation may be neglected.

58
EXAMPLES:
A solute that forms cubic crystals is to be
precipitated from solution at a rate of 10,000 lb
of solid (dry basis) per hour using 1,000 lb/h of
seed crystals. If no nucleation occurs and the
seed crystals have the following distribution,
determine the product size distribution.

Tyler Sieve Mesh Weight Fraction Retained

– 48 + 65 0.10
– 65 + 100 0.30
– 100 + 150 0.50
– 150 + 200 0.05
– 200 + 270 0.05
59
EXERCISES:
One ton of Na2S2O3•5H2O is to be crystallized per hour
by cooling a solution containing 56.5% Na2S2O3 to 30°C
in a Swenson-Walker crystallizer. Evaporation is
negligible. The product is to be sized closely to
approximately 14 mesh. Seed crystals closely sized to
20 mesh are introduced with the solution as it enters
the crystallizer. How many tons of seed crystals and
how many tons of solutions are required per hour? At
30°C, solubility of Na2S2O3 is 83 parts per 100 parts
water.

60
EXERCISES:
Trisodium phosphate is to be recovered as Na3PO4•12H2O
from a 35 wt% solution originally at 190°F by cooling and
seeding in a Swenson-Walker crystallizer. From 20,000 lb/h
feed, 7,000 lb/h of product crystals in addition to the seed
crystals are to be obtained. Seed crystals fed at a rate of 500
lb/h have the following size range:
Weight Fraction (%) Size Range, mm
10 – 0.500 + 0.250
20 – 0.250 + 0.130
40 – 0.130 + 0.065
30 – 0.065 + 0.025
a. Latent heat of crystallization of trisodium phosphate is
27,500 BTU/lbmol. Specific heat for the trisodium
phosphate solution may be taken as 0.8 BTU/lb·°F.
b. Estimate the product particle size distribution 61

c. To what temperature must the solution be cooled, and

what will be the cooling duty in BTU/h
 MSMPR CRYSTALLIZER
 After knowing the theoretical yield of the crystallizer
from the material and energy balances, what
remains to be estimated is the crystal size
distribution (CSD) of the product.
 An idealized crystallizer known as mixed-
suspension mixed-product removal (MSMPR)
Model has served well as a basis for identifying the
kinetic parameters and showing how knowledge of
them can be applied to calculate the performance of
the crystallizer.
 MSMPR CRYSTALLIZER
Assumptions:
 The operation is steady-state.
 At all times, the crystallizer contains a mixed-
suspension magma, with no product classification.
 At all times, uniform saturation exists throughout
the magma.
 The ΔL law of crystal growth applies.

 No size-classified withdrawal system is used.

 There are no crystals in the feed.
 The product magma leaves the crystallizer in
equilibrium, so the mother liquor in the product
magma is saturated.
 No product breakage into finite particle size occurs.
 MSMPR CRYSTALLIZER
Crystal-Population Density Function n
 Plot of the total cumulative number of crystals
N/VML per unit volume (usually 1 L) of size L and
smaller versus this size L. The slope d(N/VML)/dL is
defined as the crystal population density n:
d  N 

 VML  1 dN
n 
dL VML dL
n – number of
crystals/(L-mm)
 Characterizes the
nuclear growth
rate of the
crystallizer.
 MSMPR CRYSTALLIZER
Crystal-Population Density Function n
 The population density n is obtained experimentally
by screen analysis of the total crystal content of a
given volume (1 L of magma suspension).
 Each sieve fraction by weight is obtained by
collection between two closely spaced and adjacent
screens. L L
Lave  1 2
L  L1  L2
2
 For a weight fraction of crystals, the volume of the
particles is: vP  aLave
3

a  shape factor of particle

 From the total weight of the crystals in this fraction,
the density, and weight of each crystal, ΔN for the
size range ΔL can be obtained.
 MSMPR CRYSTALLIZER
Population Material Balance
 For the size range dL, the number of crystals dN is:
dN  nVML dL
 For a time interval Δt, the number of crystals
withdrawn is: ndL
 For a time interval Δt, the volume of mother liquor
withdrawn is:
Qt
 The number of crystals in the crystallizer is:
ndL
 The volume of mother liquor in the crystallizer is:
VML
 MSMPR CRYSTALLIZER
Population Material Balance
 Perfect Mixing Assumption for the Magma:
number of crystals withdrawn number of crystals in crystallizer

Vol. of ML withdrawn Vol. of ML in crystallizer
number of crystals withdrawn Vol. of ML withdrawn

number of crystals in crystallizer Vol. of ML in crystallizer
ndL n Qt
  
ndL n VML
 From the ΔL law: L  G t
 The population balance equation becomes:
n Q L n Q n dn Q n
     
n VML G L VML G dL VML G
 MSMPR CRYSTALLIZER
Population Material Balance
dn Q n
 
dL VML G
VML
 The residence time in the crystallizer: 
Q
dn n dn 1 n dn 1 L
 
dL G n

G
dL n0 n   G 
0
dL

L
ln n    ln n0
G
 where n0 is the population of the nuclei when L = 0, n
is the population when the size is L, and V/Q or τ is
the retention time in h in the crystallizer.
 MSMPR CRYSTALLIZER
Population Material Balance
L
ln n    ln n0
G
 Plot of ln n vs L where the slope is –1/Gτ and the
y-intercept is ln n0
Average Particle Size and Nucleation Rate
 Average size, La: La  3.67G
 Predominant size, Ld: Ld  3.0G
 Nucleation Rate, B0
dN dN dL
lim  lim  B 0  Gn0
L 0 dt L 0 dL dt
EXAMPLES:
Calculate the population density and
nucleation growth rates for crystal samples of
urea from screen analysis. The slurry density (g
of crystals) is 450 g/L, the crystal shape factor
is a = 1.00, the crystal density is 1.335 g/cm3,
and the residence time is 3.38 h. The screen
analysis is as follows:
Tyler Sieve Mesh Weight Percent Retained
– 14 + 20 4.4
– 20 + 28 14.4
– 28 + 35 24.2
– 35 + 48 31.6
– 48 + 65 15.5
70
– 65 + 100 7.4
– 100 2.5