PROSES

PEMISAHAN 1
CHE223

CRYSTALLIZATION
(4)

Nani Indraswati

3 May 2012 Jurusan Teknik Kimia UKWM 1

 CRYSTALLIZATION
Heat balance

Using specific-heat and heat of crystallization data :

Heat removed to cool the feed solution from

T1 (Tfeed) to T2 (Tcrystallization) without any
solid phase precipitating out
+ heat liberated when crystals are formed
(heat of crystallization) at T2
= heat lost through walls + latent heat of
evaporation + heat removed by cooling
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Example 12.11-2

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Example
Heat removal in crystallization cooling of lactose
Lactose syrup is concentrated to 8 g lactose per 10 g of water
and then run into a crystallizing vat which contains 2500 kg of
the syrup.
In this vat, containing 2500 kg of syrup, it is cooled from 57°C
to 10°C. Lactose crystallizes with one molecule of water of
crystallization.
The specific heat of the lactose solution is 3470 J/(kg)(°C).
The heat of solution for lactose monohydrate is -15,500 kJ/
mol.
The molecular weight of lactose monohydrate is 360 and the
solubility of lactose at 10°C is 1.5 g / 10 g water.
Assume that 1% of the water evaporates and that the heat
loss through the vat walls is 4 x 104 kJ.
Calculate the heat to be removed in the cooling process.

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 ADIABATIC VACUUM
CRYSTALLIZER

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CRYSTALLIZATION: Mass Balance
H2O
Vapor Magma
V kg/h M kg/h
Feed F kg/h
Crystals C kg/h
Crystallizer
Mother liquor L kg/h
(saturated solution)
Feed F = magma M + vapor V
Magma M = crystals C + mother liquor L
Solid balance Overall material balance
FxF  MxM  LxL  CxC F LC V M V
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Adiabatic evaporator-vacuum
crystallizer: Heat balance
FhF  LhL  ChC  VHV
 Adiabatic operation :
→Q=0 or
 F = rate of feed, kg/h FhF  MhM  VHV
 L = rate of mother liquor , kg/h
 C = rate of crystals, kg/h
 M = rate of magma, kg/h
 V = rate of vapor (superheated), kg/h
 H, h = enthalpy, J/kg

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 TCryst

3 May 2012 xL
Jurusan Teknik Kimia UKWM xM xC 8
hF Enthalpy-
concentration
diagram

System
MgSO4 - H2O

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xL
xF xM xC
Adiabatic evaporator-vacuum crystallizer
F=M+V
M=L+C
M a

V Vapor V F ab
M a
 V b
V b 
F ab
C p
C p 
 M pq
L q
a L q

M pq
Mother
liquor L Feed F F = feed
b Crystals C L = mother liquor
p C = crystals
q
M = magma
3 May 2012 Magma MJurusan Teknik Kimia UKWM V =vapor 10
Example

C
C = 2012
3 May 10000 lb  Jurusan Teknik Kimia UKWM
lb crystal/lb mother liquor11
L
 Example
The vapor leave the crystallizer at 86oF (superheated vapor
→ saturated at 84oF + BPR 2oF)

1.884 kJ/kg.oC

HV = Hsat + (Cpsuperheated vapor )( oC or oF superheat)

enthalpy of saturated vapor at TSat BPR

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 Vapor V

F =M+V
M=C +L
Feed F
mother
Magma M
liquor L
Crystal C

xL xM xC
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 1098 vapor
C 0.224 fe
 
L 1 de
C 0.224 fe
 
M 1 0.224 fd

isotherm 86oF
V be

mother M ab
feed
-43 liquor magma
-62.4
-149
crystals
0.285 0.488

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hF Enthalpy-
concentration
diagram

System
MgSO4 - H2O

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xL
xF xM xC
 C 0.224
  C  10000 lb
L 1 L

C L M
d f
Basis: 1 lb mother liq L
1 x 0.285
0.322
point e
d f

V be M V
 V=
M ab
=F
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 1098 vapor
C 0.224 fe
 
L 1 de
C 0.224 fe
 
M 1 0.224 fd

isotherm 86oF
V be

mother M ab
feed
-21 liquor magma
-62.4 crystals
0.285 0.488

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Adiabatic evaporator-vacuum crystallizer

M a

V Vapor F ab
M a
 V b
V b 
F ab
C p
C p 
 M pq
L q
a L q

M pq
Mother
liquor Feed F = feed
b crystals L = mother liquor
p C = crystals
q
M = magma
3 May 2012 magma
Jurusan Teknik Kimia UKWM
V =vapor 18
 Adiabatic evaporator-vacuum crystallizer
 If TF is increased at the same P
 the point F(xF,hF) moves upward on a vertical line
 the point M move downward to the right
 ratio C/M will increase

 If lower operating P is used at the same TF and xF

 lower operating temperature
 HV decreases → point V(y,H) will move downward
 the line LM will move downward
 point L will move to the left along curve A
 the point C moves down on the vertical line
 the point M shifts downward to the right
 ratio C/M will increase

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Problem
 Larutan MgSO4 30% berat pada suhu
220oF dialirkan ke suatu crystallizer
dengan laju 3500 lb/jam.
Suhu pada crystallizer 86oF
Larutan jenuh MgSO4 mempunyai
kenaikan titik didih sebesar 2oF.
Hitung laju kristal yang dihasilkan

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Crystallization Mechanism

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 CRYSTALLIZATION
Crystal growth

 Rate of crystal growth: the distance moved per

unit time in a direction perpendicular to the face
 Solute molecules A reach the face by diffusion from
the super-saturation bulk solution to the surface
_
N
A  k (y  y' )........... .......... ....... 12.12 - 1
A y A A
k y  mass transfer coefficient, kmol/ s m2 mol frac 
_
NA  mass tranfer rate of solute A. kmol A/s
A  surface area, m2
y A3 Maysupersatur
2012
ation concentrat ion (mole fraction of solute A) of bulk solution
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y 'A  solute concentrat ion (mole fraction of solute A) at the surface

CRYSTALLIZATION
Crystal growth

_
N
A  k (C  C' )
A c A A
k c  mass transfer coefficient
_
NA  mass tranfer rate of solute A, kmol A/s
A  surface area
C A  supersatur ation concentrat ion of bulk solution
C'A  solute concentrat ion at the surface

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 CRYSTALLIZATION
Crystal growth
 At the surface : integration reaction of the
molecules into the space lattice
_
N
A  k (y '  y ) .......... ......... 12.12 - 2
A S A Ae
k S  surface reaction coefficient, kmol/(s)(m 2 )(mol frac)
N A  mass tranfer rate of solute A, kmol/s
A  surface area
y Ae  saturation concentrat ion (mole fraction) of A
y A  solute concentrat ion (mole fraction) of A at the surface
'

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CRYSTALLIZATION
Crystal growth

N
A  k (C '  C ) .......... ......... 12.12 - 2
A sc A Ae
k sc  surface reaction coefficient, kmol/(s)(m 2 )( mol / m 3 )
NA  mass tranfer rate of solute A, kmol/s
A  surface area
C Ae  saturation concentrat ion
C A  solute concentrat ion at the surface
'

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CRYSTALLIZATION
Crystal growth
 Solution must be super-saturated for
the diffusion (12.12-1) & interfacial
(12.12-2) steps to proceed

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CRYSTALLIZATION
Crystal growth

 Combining eq. 12.12-1 & 12.12-2 :

_
NA (y A  yAe )
 .  K(y A  y Ae )......... ......... 12.12 - 3
A 1  1
ky kS
K  overall transfer coefficient
 ky predicted by methods for mass transfer to
suspensions of small particles (sect. 7.4), mass
transfer through fixed bed or fluidized bed

3 May 2012 Jurusan Teknik Kimia UKWM 27

CRYSTALLIZATION
Crystal growth

_
NA (C A  CAe )
 .  K c (C A  CAe )
A 1  1
kC k SC
K c  overall transfer coefficient

 kc predicted by methods for mass transfer to suspensions

of small particles (sect. 7.4), mass transfer through fixed
bed or fluidized bed
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 CRYSTALLIZATION
Crystal growth

 Crystal growth is measured as the increase

in length DL (linear dimension of one crystal,
mm)
 In the same environmental conditions, DL is
independent of initial crystal size
ΔL  D2  D1  Gt 2  t1 
G  growth rate constant
D  linear dimension of crystal at time t

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