CRYSTALLIZATION

- a unit operation in which solid particles are formed from a liquid solution.
- involves simultaneous heat and mass transfer
- is a solid – liquid operation used to separate solutes from solution in the form of crystals; wherein mass is transferred
from the liquid phase (solution) to solid phase (crystal surface).

Crystallization in process industry are usually from solution (plant extracts to saleable crystals) or melt (polymerization
crystals) where almost pure product from relatively impure solutions in a single processing step in the form of crystals of
desired size range are carried out at low temperatures.

Advantages over other unit operations:

1. high purity product
2. requires relatively low temperature operations (energy requirement is low)
3. high yield can be obtained in single processing step
4. convenience in storage (packing and storing)
5. increased shelf - life

Disadvantages:
1. yield of given product
2. purity of product
3. energy requirements
4. shape and size of crystals
5. uniformity or size distribution
6. rate of crystal production
7. caking

Types of Crystallization process:

1. concentration of solution by evaporation
2. crystallization by cooling
3. combined cooling and evaporation (adiabatic evaporation)
4. salting out process

Design Considerations:
1. phase diagrams
2. crystallization process
3. crystal characteristics
4. equipment

In crystallization process, the equilibrium will be reached when the solution is saturated and the equilibrium data are given in
the form of solubility curves. The solubility of solute in a given solvent depends on the nature of solute, the nature of solvent
and the prevailing temperature.

SOLUBILITY
- the concentration of the solute in a saturated solution at a given temperature

CAKING OF CRYSTALS:
Caking of crystalline materials is caused by a small amount of dissolution occurring at the surface of crystals and subsequent
re-evaporation of the solvent.

MAGMA
- a two-phase mixture of mother liquor and crystals that occupy the crystallizer and in turn withdrawn as product

Effects of impurities on crystal formation:

- soluble impurities may get adsorbed on the surface of the crystal nuclei or crystals – nucleation sites and retard the
rate of nucleation and crystal growth
- the shape of crystal may get modified as adsorption of impurities may occur preferentially on a particular face

The impurities may decrease the rate of crystal growth. In some cases, it is desirable to add small quantity of glue or tannin to
boiler feed water to prevent nucleation and growth of calcium carbonate and thus reduce scaling.

ChE 421: Heat and Mass Transfer

Engr. MMM Boado
Classification of Crystallizers:
Crystallizers may be classified on the basis of mode of operation. These may be operated batch-wise or continuous. Based on
supersaturation;

1. Supersaturation by cooling alone;

a) Batch – Agitated tank crystallizers
b) Continuous – Swenson – Walker crystallizer

2. Supersaturation by adiabatic evaporation and cooling;

a) Vacuum crystallizer

3. Supersaturation by evaporation;
a) Krystal crystallizer (Oslo crystallizer)
b) Draft – tube crystallizer

CRYSTALLIZATION DIAGRAM:
Evaporated solvent, V

Feed Mother liquor, L

xF CRYSTALLLIZER

Crystals, C

F – mass flow rate of feed, kg/h xF – mass fraction of anhydrous solute in feed
C – crystals product, kg/h V – mass flow rate of evaporated solvent, kg/h
L – mass flowrate of mother liquor L’ – mass flowrate of solvent in mother liquor
X’ – solubility at the final temperature M – molecular weight

OVERALL BALANCE:
𝐹 =𝑉+𝐿+𝐶

COMPONENT BALANCE:
𝑀𝐻2𝑂
𝒔𝒐𝒍𝒗𝒆𝒏𝒕: 𝐹(1 − 𝑥𝐹 ) = 𝑉 + 𝐿′ + ( ∙ 𝐶)
𝑀ℎ𝑦𝑑𝑟𝑎𝑡𝑒 𝑐𝑟𝑦𝑠𝑡𝑎𝑙
𝑀𝑎𝑛ℎ𝑦𝑑𝑟𝑜𝑢𝑠 𝑠𝑎𝑙𝑡
𝒔𝒐𝒍𝒖𝒕𝒆: 𝐹(𝑥𝐹 ) = ( ∙ 𝐶) + (𝐿′ 𝑋 ′ )
𝑀ℎ𝑦𝑑𝑟𝑎𝑡𝑒 𝑐𝑟𝑦𝑠𝑡𝑎𝑙
𝑎𝑚𝑜𝑢𝑛𝑡 𝑠𝑜𝑙𝑢𝑡𝑒 𝑐𝑟𝑦𝑠𝑡𝑎𝑙𝑖𝑧𝑒𝑑 𝑎𝑚𝑜𝑢𝑛𝑡 𝑐𝑟𝑦𝑠𝑡𝑎𝑙𝑠 𝑓𝑜𝑟𝑚𝑒𝑑
𝑦𝑖𝑒𝑙𝑑 = 𝑂𝑅
𝑎𝑚𝑜𝑢𝑛𝑡 𝑜𝑓 𝑠𝑜𝑙𝑢𝑡𝑒 𝑖𝑛 𝑓𝑒𝑒𝑑 𝑎𝑚𝑜𝑢𝑛𝑡 𝑜𝑓 𝑓𝑒𝑒𝑑
*note how yield was stated or described

ENERGY BALANCE:
ℎ𝑒𝑎𝑡 𝑜𝑓 𝑐𝑟𝑦𝑠𝑡𝑎𝑙𝑙𝑖𝑧𝑡𝑎𝑖𝑜𝑛 = −ℎ𝑒𝑎𝑡 𝑜𝑓 𝑠𝑜𝑙𝑢𝑡𝑖𝑜𝑛

1. Cooling crystallizer with no evaporation of solvent

𝑡𝑜𝑡𝑎𝑙 ℎ𝑒𝑎𝑡 𝑟𝑒𝑚𝑜𝑣𝑒𝑑 𝑓𝑟𝑜𝑚 𝑠𝑦𝑠𝑡𝑒𝑚 = ℎ𝑒𝑎𝑡 𝑓𝑟𝑜𝑚 𝑓𝑒𝑒𝑑 𝑠𝑜𝑙𝑢𝑡𝑖𝑜𝑛 + ℎ𝑒𝑎𝑡 𝑜𝑓 𝑐𝑟𝑦𝑠𝑡𝑎𝑙𝑙𝑖𝑧𝑎𝑡𝑖𝑜𝑛
𝑄 = 𝐹𝐶𝑝𝐹 (𝑇2 − 𝑇1 ) + 𝐶𝜆𝑐

2. Cooling crystallizer with evaporation during cooling

𝑛𝑒𝑡 ℎ𝑒𝑎𝑡 𝑟𝑒𝑚𝑜𝑣𝑒𝑑 𝑓𝑟𝑜𝑚 𝑠𝑦𝑠𝑡𝑒𝑚 = ℎ𝑒𝑎𝑡 𝑓𝑟𝑜𝑚 𝑓𝑒𝑒𝑑 𝑠𝑜𝑙𝑢𝑡𝑖𝑜𝑛 + ℎ𝑒𝑎𝑡 𝑜𝑓 𝑐𝑟𝑦𝑠𝑡𝑎𝑙𝑙𝑖𝑧𝑎𝑡𝑖𝑜𝑛 − ℎ𝑒𝑎𝑡 𝑓𝑟𝑜𝑚 𝑒𝑣𝑎𝑝𝑜𝑟𝑎𝑡𝑒𝑑 𝑠𝑜𝑙𝑣𝑒𝑛𝑡
𝑄 = 𝐹𝐶𝑝𝐹 (𝑇2 − 𝑇1 ) + 𝐶𝜆𝑐 − 𝑉𝜆𝑣

ChE 421: Heat and Mass Transfer

Engr. MMM Boado
Problems on Crystallization:
1. Calculate the yield of MgSO4.7H2O crystals when 1000 kg of saturated solution at 353 K is cooled to 303K assuming 10% of
the water is lost by evaporation during cooling.
Data: solubility of MgSO4 at 353K = 64.2 kg/100 kg water
solubility of MgSO4 at 303K = 40.8 kg/100 kg water

2. A hot solution containing 5000 kg of Na2CO3 and water with a concentration of 25% by weight Na2CO3 is cooled to 293 K
and crystals of Na2CO3.10H2O are precipitated. At 293 K, the solubility is 21.5 kg anhydrous Na 2CO3 per 100 kg of water.
Calculate the yield of Na2CO3 crystals obtained if 5% of original water in the system evaporates on cooling.

3. A hot solution containing 2000 kg of MgSO4 and water at 330K and with a concentration of 30% by weight MgSO4 is cooled
to 293 K and MgSO4.7H2O crystals are formed. The solubility at 293 K is 35.5 kg MgSO4/100 kg water. The average heat
capacity of the feed solution is 2.93 kJ/kg.K. The heat of solution at 293 K is – 13.31 x 103 kJ/kmol MgSO4.7H2O. calculate
the yield of crystals and make the heat balance. Assume no water is vaporized.

4. A solution containing 500 kg of Na2SO4 and 2500 kg of water is cooled from 333K to 283 K in an agitated mild steel vessel
weighing 750 kg. at 283 K, the solubility of anhydrous salt is 8.9 kg per 100 kg of water. Na2SO4 crystallizes as Glauber’s
salt. If 2% of the original water is lost by evaporation during cooling, calculate the heat that must be removed and yield of
hydrated crystals in kg.
Additional data: heat capacity of solution = 3.6 kJ/kg.K
heat capacity of mild steel = 0.5 kJ/kg.K
heat of solution = - 78.5 MJ/kmol
latent heat of vaporization of water = 2395 kJ/kg

5. A saturated solution of sodium sulfate is available at a temperature of 30°C. Find out the weight of Na 2SO4·10H2O formed
if 1000kg of this solution is cooled to 10°C.

6. A solution of barium nitrate at 40°C. Find out the crystal yield of 2000kg of original solution if it is cooled to 10°C.

7. A crystallizer is charged with 7500 kg of an aqueous solution at 377K, 29.6% by weight of which is anhydrous sodium
sulfate. The solution is cooled where 5% of the initial water is lost by evaporation. Decahydrate crystals were formed as a
result. Calculate the yield of crystals and the quantity of mother liquor if it is found to contain 18.3% by weight anhydrous
Na2SO4.

8. An adiabatic vacuum crystallizer is to be used to produce 10 tons/h of copperas crystals. The feed is a solution containing
38.9 parts FeSO4 per 100 H2O and enters at 343K. The crystallizer vacuum is such that it produces crystallization
temperature of 299.7K. Find the feed rate to the crystallizer. The saturated solution at 299.7K contains 30.2 FeSO 4 per 100
H2O. The following enthalpy data are available:
L = - 5.57 kJ/kg F = 108.9 kJ/kg
C = - 211 kJ/kg

9. A solution containing 23 per cent by mass of sodium phosphate is cooled from 313 to 298 K in a Swenson-Walker
crystallizer to form crystals of Na3PO4.12H2O. The solubility of Na3PO4 at 298 K is 15.5 kg/100 kg water, and the required
product rate of crystals is 0.063 kg/s. The mean heat capacity of the solution is 3.2 kJ/kg K and the heat of crystallization is
146.5 kJ/kg. If cooling water enters and leaves at 288 and 293 K, respectively, and the overall coefficient of heat transfer is
140 W/m2 K, what length of crystallizer is required?

10. A Swenson-Walker crystallizer has to produce 800 kg/h of Glauber’s salt. The saturated solution enters the crystallizer at
49°C and the slurry leaves at 27°C. Cooling water enters the crystallizer jacket at 15°C and leaves at 21°C. The overall heat
transfer coefficient has been estimated to be 175 kcal/hr·m2·°C. There are 1.3m2 of cooling surface per meter length of
crystallizer. (a) estimate the cooling water requirement in kg/h and (b) determine the number of crystallizer sections if
each will be 3m long. The specific heat of the initial solution is 0.5 kcal/kg °C and the heat of crystallization is 18.5 kcal/kg.

ChE 421: Heat and Mass Transfer

Engr. MMM Boado
Solubility of salts

Enthalpy – Concentration diagram of CaCl2

ChE 421: Heat and Mass Transfer

Engr. MMM Boado
Phase diagram of MgSO4

Enthalpy – Concentration diagram of MgSO4

ChE 421: Heat and Mass Transfer

Engr. MMM Boado