Lecture 6 Crystallization

CRYSTALLIZATION
a process where solid particles are formed

from a homogeneous phase
a solid-liquid separation process
for control:
– yield of crystals
– purity of crystals
– sizes and shapes of crystals
A crystal is a highly organized
array of atoms, molecules, or ions
arranged in three-dimensional
space lattices.
Common methods of reaching
supersaturation
Cooling (with some exceptions)
– achieved near a heat-transfer surface
Solvent evaporation
– achieved near a heat-transfer surface
Drowning
– Addition of nonsolvent, which decreases the solubility
of the solid.
Chemical reaction
– Decreases the solubility of the dissolved solvent,
leading to supersaturation
Progression of
crystallization
EQUILIBRIUM SOLUBILITY CURVES FOR
CRYSTALLIZATION
Fig. 18-56 (Perry’s CHE Handbook, 7th Ed.) –

Solubility of MgSO4xH2O in water at 1 atm
Fig. 12.11-1 (Geankoplis, 4th Ed.) – Solubility of
Na2S2O3 in water at 1 atm
Fig. 19.27 (Foust et al., 2nd Ed.) – Solubility of
Na2SO4 in water at 1atm
Fig. 19.28 (Foust et al., 2nd Ed.) – Enthalpy-
concentration diagram for the Na2SO4 - H2O
system at 1 atm
Fig. 19.29 (Foust et al., 2nd Ed.) – Enthalpy
concentration diagram for the CaCl2 - H2O
system at 1 atm
Solubilities
of several
solids
MATERIAL BALANCES: YIELD OF CRYSTALS
S
10,000 KG
Concentrated solution
30% Na2CO3
T = 293 K
Solubility :
21.5 kg Na2CO3 / 100 kg H2O
C
Na2CO310H2O
Solute Balance
 Ma    Mh  Ma 
Fx  C   F1  x F   V  C S'
F  Mh    Mh 
Total Balance
F  V  M  V CS
C = mass of crystals in the product magma per unit time
Ma = molecular weight of anhydrous salt or crystal
Mh = molecular weight of hydrated crystal
xF = mass fraction of anhydrous solute in feed
S’ = solubility of the anhydrous solute at product temperature
= expressed as a weight ratio of anhydrous salt to solvent
F = total mass of feed solution per unit time
V = evaporation rate in mass of solvent per unit time
S = mass of saturated solution produced per unit time
M = total mass of product magma produced per unit time
= mass of crystals formed + saturated solution
HEAT BALANCE:
H F  HC  q  H L  H V
q = total heat absorbed in the crystallization/evaporation process

HF = total enthalpy of entering solution at TF, which is read off
enthalpy-concentration diagram
HM = total enthalpy of the crystals and saturated solution in the
product magma at the final temperature, TL
HV = total enthalpy of the vapor
HC = total heat of crystallization
= positive if crystallization is exothermic
= evaluated as the negative of the heat of solution
HEAT BALANCE (Vacuum Operation)
Vλ V  H F  H L   H C
V = latent heat of vaporization of the solvent
HF – HL = sensible heat drop

Classification of Crystallization Equipment
According to mode of operation

– Batch
– Continuous
According to method by which supersaturation
is achieved
– Crystallizers that obtain precipitation by cooling a
concentrated, hot solution
Agitated batch crystallizers
Swenson-Walker crystallizers
– Crystallizers that obtain precipitation by evaporating a
solution
Salting out evaporators
Draft-tube evaporators
Oslo crystallizers (e.g., ‘Krystal’ crystallizer for ammonium sulfate
production)
– Crystallizers that obtain precipitation by adiabatic
evaporation and cooling
Vacuum crystallizers
TANK CRYSTALLIZERS
•Hot, saturated solutions are allowed to cool in open tanks. After
crystallization, the mother liquor is drained and the crystals are
collected.
•Controlling nucleation and the size of the crystals is difficult.
•The crystallization is essentially just "allowed to happen".
•Heat transfer coils and agitation can be used.
•Labor costs are high, thus this type of crystallization is typically
used only in the fine chemical or pharmaceutical industries where
the product value and preservation can justify the high operating
costs.
SCRAPED-SURFACE CRYSTALLIZERS
•An example may be the Swenson-Walker crystallizer
consisting of a trough about 2 feet wide with a semi-circular
bottom.
•The outside is jacketed with cooling coils and an agitator
blade gently passes close to the trough wall removing crystals
that grow on the vessel wall.
FORCED CIRCULATING LIQUID EVAPORATOR-

CRYSTALLIZER
•combines crystallization and evaporation, thus the driving
forces toward supersaturation
FORCED CIRCULATING
LIQUID EVAPORATOR-
CRYSTALLIZER
•The heated liquid flows into

the vapor space of the
crystallization vessel. Flash
evaporation occurs, reducing
the amount of solvent in the
solution, thus driving the
mother liquor towards
supersaturation.
•The supersaturated liquor
flows down through a tube,
then up through a fluidized area
of crystals and liquor where
crystallization takes place via
secondary nucleation. Larger
product crystals are withdrawn
while the liquor is recycled,
mixed with the feed, and
reheated.
CIRCULATING MAGMA VACUUM CRYSTALLIZER
•The crystal/solution mixture (magma) is circulated out of the
vessel body.
•The magma is heated gently and mixed back into the vessel.
•A vacuum in the vapor space causes boiling at the surface of
the liquid.
CIRCULATING MAGMA
VACUUM CRYSTALLIZER
Crystallizer Design
CRYSTAL SIZE DISTRIBUTION
Crystallization is operated to maximize crystal

growth and restrict nucleation.
Product CSD is based on kinetics and nucleation
growth of crystals.
If it is assumed that nucleation does not occur
and that the initial CSD is not known, a rough
estimation of CSD can be calculated.
The McCabe L law is commonly used to
calculate the final CSD if initial CSD in known.
The L Law
If all crystals in magma grow in a uniform
supersaturation field and at the same temperature
and if all crystals grow from birth at the rate
governed by the supersaturation, then all crystals
are not only invariant but also have the same
growth rate that is independent of size.
L = Gt
G ≠ f(L) : growth rate
t : time
Calculation of CSD for a seeded crystallizer
L P  L S  ΔL
LP = characteristic crystal product dimension

LS = characteristic crystal seed dimension
L = change in dimension; constant throughout the
range of sizes present
Relationship between seed mass (mS) and product mass (mP)
m P  ' ρL  ρL S  ΔL

3 3
P
m S   ' ρL3S
3
 ΔL 
Combining: m P  m S  1  
 LS 
’ = shape factor (different from the usual
shape factor)
 = particle density
For the entire crystal mass:
3
 ΔL 
mP mS
0 dm P  0  1  L S  dm s  m P
MSMPR
MSMPR or MIXED-SUSPENSION MIXED-PRODUCT REMOVAL

MODEL
– An idealized crystallizer model, which is a basis
for identifying the kinetic parameters and showing
how knowledge of them can be applied to
calculate the performance of such crystallizer.
MSMPR Assumptions
Steady-state
Crystallizer contains a mixed-suspension magma at all
times, with no product classification
Uniform supersaturation exists throughout the magma at
all times
L law of crystal growth applies
No size-classified withdrawal system
No crystals in the feed
Mother liquor in the product magma is saturated
(equilibrium)
No crystal breakage into finite particle size
CRYSTAL POPULATION-DENSITY FUNCTION
dN ΔN
n 
dL ΔL
N dN
n
dL
L
Assumptions:
•In t time, nL crystals are withdrawn.
•The effluent composition in the outflow is Q L/h, which is the same as
that in the crystallizer of volume V.
 Δn ΔL Q Δt

n ΔL V
Recall the L law (equation 5). If G is in mm/h:
 Δn Q ΔL

n VG
As both L and n approach 0, and integrating,
n
dn 1
L
 L 
n  n exp 
0 n Gτ 0 dL
  
0
n
 Gτ 
where  = V/Q, which is the total retention time or holding time (in hours)
in the crystallizer, and n0 is the population of nuclei when L = 0.
A solution of 500 kg of Na2SO4 in 2500 kg of
water is cooled from 333 to 283 K in an agitated
mild steel vessel of mass 750 kg, the specific
heat of steel being 0.5 kJ/kg-K. At 283 K the
stable crystalline phase Na2SO410H2O and at
291 K the heat of solution is -78.5 MJ/kgmol.
The mean heat capacity of the solution is 3.6
kJ/kg-K. If, during cooling, 2% by mass of the
water is lost by evaporation, estimate the yield of
crystals formed and the heat to be removed. The
solubility of the anhydrous salt at 283 K is 8.9
kg/100 kg water.

Lecture 6 Crystallization

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CRYSTALLIZATION

a process where solid particles are formed

Fig. 18-56 (Perry’s CHE Handbook, 7th Ed.) –

q = total heat absorbed in the crystallization/evaporation process

V = latent heat of vaporization of the solvent

HF – HL = sensible heat drop

According to mode of operation

FORCED CIRCULATING LIQUID EVAPORATOR-

•The heated liquid flows into

Crystallization is operated to maximize crystal

LP = characteristic crystal product dimension

m P  ' ρL  ρL S  ΔL

MSMPR or MIXED-SUSPENSION MIXED-PRODUCT REMOVAL

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