PROSES PEMISAHAN 1

CHE223

CRYSTALLIZATION
(4)
Nani Indraswati

3 May 2012

Jurusan Teknik Kimia UKWM

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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Jurusan Teknik Kimia UKWM

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 57C to 10C. 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 10C 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

3 May 2012

Jurusan Teknik Kimia UKWM

CRYSTALLIZATION: Mass Balance

H2O Vapor V kg/h Feed F kg/h Crystallizer

Magma M kg/h
Crystals C kg/h Mother liquor L kg/h (saturated solution)

Feed F = magma M + vapor V Magma M = crystals C + mother liquor L

Solid balance Fx F Mx M Lx L CxC

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Overallmaterialbalance F LCV MV
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Jurusan Teknik Kimia UKWM

Adiabatic evaporator-vacuum crystallizer: Heat balance

Adiabatic operation :
Q=0

FhF LhL ChC VHV or FhF MhM VHV

F = rate of feed, kg/h 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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Jurusan Teknik Kimia UKWM

TCryst

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Jurusan Teknik Kimia UKWM

xL

xM

xC

hF

Enthalpyconcentration diagram System MgSO4 - H2O

3 May 2012

xL

Jurusan Teknik Kimia UKWM

xF xM

xC

Adiabatic evaporator-vacuum crystallizer

F=M+V M=L+C

Vapor V

M a V b C p L q

a Mother liquor L p
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M F V F C M L M

a ab b ab p pq q pq

Feed F

b
q

Crystals C

Magma M Jurusan Teknik Kimia UKWM

F = feed L = mother liquor C = crystals M = magma 10 V =vapor

Example

C = 2012 3 May 10000 lb

C L

Jurusan Teknik Kimia UKWM

lb crystal/lb mother liquor11

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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Jurusan Teknik Kimia UKWM

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Vapor V

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

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 mother liquor
-149 0.285
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-43 -62.4

feed magma

V be M ab
crystals

0.488
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hF

Enthalpyconcentration diagram System MgSO4 - H2O

3 May 2012

xL

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xF xM

xC

C 0.224 C 10000 lb L 1
C L M

d
Basis: 1 lb mother liq L

1 x 0.285
0.322

point e

V be M ab
3 May 2012

M V=

=F

Jurusan Teknik Kimia UKWM F V

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1098

vapor

C 0.224 fe L 1 de C 0.224 fe M 1 0.224 fd

isotherm 86oF mother liquor
0.285
3 May 2012

-21 -62.4

feed magma

V be M ab
crystals

0.488
Jurusan Teknik Kimia UKWM 17

Adiabatic evaporator-vacuum crystallizer

M F V F C M L M a ab b ab p pq q pq

Vapor

M a V b C p L q

a Mother liquor p
3 May 2012

Feed

b
q

crystals

magma Jurusan Teknik Kimia UKWM

F = feed L = mother liquor C = crystals M = magma 18 V =vapor

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 y A 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 supersatur ation concentrat Teknik Kimia UKWM ion (mole fraction of solute A) of bulk solution May 2012 Jurusan 22 y 'A solute concentrat (mole fraction of solute A) at the surface ion
_

CRYSTALLIZATION
Crystal growth
_ N A k (C C' ) c A 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 of bulk solution ion C'A solute concentrat at the surface ion
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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 Ae S A A
k S surface reaction coefficient, kmol/(s)(m2 )(mol frac) N A mass tranfer rate of solute A, kmol/s A surface area y Ae saturationconcentrat (mole fraction)of A ion y A solute concentrat (mole fraction)of A at the surface ion
'
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CRYSTALLIZATION
Crystal growth
N A k (C ' C ) ...................12.12 - 2 sc A Ae A
k sc surface reactioncoefficient, kmol/(s)(m2 )(mol / m3 ) NA mass tranfer rate of solute A, kmol/s A surface area C Ae saturationconcentrat ion C A solute concentrat at the surface ion
'

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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 1 1 A ky kS K overall transfer coefficien t

ky 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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3 May 2012

CRYSTALLIZATION
Crystal growth

NA (CA CAe ) . K c (CA CAe ) 1 1 A 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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3 May 2012

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

L D2 D1 Gt 2 t1 G growth rate constant D linear dimension of crystalat time t

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