Crystallization

Crystallization formation of solid crystals from a homogenous solution

Crystallization solid-liquid separation technique
Crystallization Unit Operation that will bring a solute out of solution as crystals by inducing supersaturation

Saturation state where a liquid contains the maximum amount of solute it can dissolve at a temperature
Supersaturation state where a liquid contains more dissolved solids (solute) that can ordinarily be
accommodated at a temperature
Solubility maximum amount of solid (solute) that can be dissolved in a given amount of solvent at a
specified temperature
o Solubility Curves

Methods of inducing Supersaturation

o Cooling applicable for solids whose solubility decreases with temperature
o Evaporation of the solvent applicable for solids whose solubility do not vary too much with
temperature or decreases with temperature
o Evaporation of the solvent with cooling applying vacuum pressure
o Drowning addition of a non-solvent to the solution which decreases the solubility of the solid
o Chemical Reaction decreases the solubility of the dissolved solid in the solvent; supersaturation
Nucleation
o Primary Nucleation formation of a new crystal nuclei
o Secondary Nucleation crystal growth is initiated with contact
o Seeding addition of nuclei where crystal growth occurs
Types of Crystallizers
o Tank Crystallizers oldest and most basic
o Scraped Surface Crystallizers (Swenson-Walker Crystallizer)
- Each unit has a length of 10ft
- The outside is jacketed where cooling water flows
- An agitator blade removes crystals that grow on the vessel wall
- Feed flows countercurrent to the cooling water
Forced Circulating Liquid Evaporator-Crystallizer
- Steam causes evaporation of the solvent in the solution

- The supersaturated liquor flows down a fluidized area of crystals and liquor where
crystallization takes place
Vacuum Crystallizer
- Vacuum in the vapor space causes boiling of the liquid
- Evaporation causes crystallization

Equation:
Scraped Surface Crystallizer (Swenson Walker)
Cooling Water

W
t2

Feed

W Cpw
t1

ML

F
XF
CF

Mother
Liquor

C
XC
LC

L
XL

Crystals

Liquor

Material Balance
=+

Overall Material Balance:

= +

Solute Balance:

(1 ) = (1 ) + (1 )

Solvent Balance:

Heat Balance
= (2 1 ) = ( ) +
Nomenclature
F
C
ML
L
w

Mass Rate
Feed
Crystals
Mother Liquor
Liquor
Water
Mass Fraction

Units
Kg/hr
Kg/hr
Kg/hr
Kg/hr
Kg/hr
Units

TF
TL
t1
t2

Temperature
Feed
Crystals
Water Inlet
Water Outlet

Heat

Units
oC
oC
oC
oC

Units

XF
XC
XL

Feed
Crystals
Liquor

g sol/g soln
g sol/g soln
g sol/g soln

CpF
Cpw
Lc
q

Feed
Water
Crystals
Heat

Vacuum Crystallizer

Material Balance
=++

Overall Material Balance:

= +

Solute Balance:
Energy Balance

= + +
(

) = 1 + 0.45

= 1

Sample Problems:
1. The solubility of ferrous sulfate in g/100g water is?
=

4
= .
4 72

2. How many crystallizer units are needed if the Swenson crystallizer is 30ft long?
*1 unit=10ft
N=30/10
N=3 units

KJ/Kg-K
KJ/Kg-K
KJ/Kg
KJ/hr

Liquid-Liquid Extraction
Liquid-Liquid Extraction
o a component in a liquid solution is separated through contact with a selective liquid solvent
o carried on by the differences in chemical properties of the feed components, such as in polarity and
hydrophobic/hydrophilic character
o produces a solvent-rich stream called the extract that contains a portion of the feed and the extractedfeed stream called the raffinate
o a separation process by phase creation or addition

o application to phase rule:

P = 2 C= 3 = F (solute, diluent, solvent)
o Commercial equipments
Stirred tanks and decanters
Specialized mixer-settlers
Agitated and nonagitated extraction columns or towers
Centrifuges

Equation:
Components:
A solute
B diluent
C solvent

La = feed rate
Vb = fresh solvent rate
x = solute fraction in L
y = solute fraction in V

Ln = raffinate rate from stage n (decreasing)

Vn = extract rate from stage n (increasing)
L = pure diluent (constant)
V = pure solvent rate (constant)
KD = distribution coefficient

Equilibrium Relation:
Y = KDX
Lx = LX
Vy = VY

=
=

=
=

Yn* = KDXn
Yn = KDXn*
Over-all Balances:
Stream Balance:
La + Vb = Lb + Va
Solute Balance:
Laxa +Vbyb = Lbxb +Vaya
LXa + VYb = LXb + VYa

V(Yb Ya) = L(Xb Xa)

=

V = V(1-y)
V = V(1+Y)
L = L(1-x)
L = L(1+X)

1+

=
1
=

1+

Xb = Xa(1-r)

Sample Problems:
1.

There are 40 kg of solute in 100 liters of water, the weight of solute that will be extracted by 30 liters of ether if the
distribution coefficient, KD=5 is?
Solution
=

conc of solute in raffinate phase

conc of solute in extract phase
40
5 = 100

30
= .

2.

A solute has a KD between water and chloroform of 5.00. Suppose we extract a 50.00-mL sample of a 0.050 M
aqueous solution of the solute with 15.00 mL of chloroform. (a) What is the separations extraction efficiency?
Solution

solute remaining in aq =
solute remaining =

V aq
K DVsolvent + Vaq

50ml
= 0.4
5(15ml) + 50ml

*Extraction efficiency is the percentage of solute moving into the extracting phase.
Extraction efficiency=1-0.4=0.6 or 60%

3. A solution contains a material M in water. M is recovered from the solution using solvent S. If 9 kg of S is
used per kg of solution and KD=3, what is the %M that will remain in the solution after solvent extraction?
Solution
*Assuming 100kg of initial solution
KD =

solute in extraction phase

solute in raffinate phase
M
9
3=
100 M
100
M=21.25%