CHE 405: Separation Processes II

Crystallization
Department of Chemical Engineering
University of Maiduguri

1
Learning Outline
Module 1: Introduction to Crystallization
• Definition and Context
• Importance of Crystal Properties
• Crystal Geometry and Classification

Module 2: Physicochemical Principles

• Equilibrium Solubility and Curves
• Hydrates and Their Solubility Behavior
• Yield Calculations and Material Balances
• Heat Effects: Heat of Crystallization & Heat Balances

Module 3: Crystallization Equipment

• Classification of Crystallizers
• Tank Crystallizers
• Scraped Surface Crystallizers
• Circulating Liquid & Magma Crystallizers

Module 4: Crystallization Theory

• Overview: Nucleation and Growth
• Nucleation Mechanisms
• Crystal Growth Mechanisms
• McCabe's ΔL Law
2
 Module 1:
Introduction to Crystallization

3
Definition and Context
Definition: A solid-liquid separation process involving mass
transfer of a solute from a liquid solution to form a pure solid
crystalline phase.

General Process: Formation of solid particles from a

homogeneous phase (liquid solution, melt, vapor).

Focus: Crystallization from liquid solution is the most

commercially important method discussed here.

Mechanism: Typically involves concentrating a solution and

cooling it below its saturation temperature (solubility limit).
Solute then precipitates out as crystals.

Example: Production of sucrose (sugar) from aqueous sugar

beet solutions.

4
Importance of Crystal Properties
Key Objectives in Commercial Physical Characteristics
Crystallization
• Size: Often specified by purchasers (e.g., large vs. small)
• Yield: Maximize the amount of solid product recovered • Shape: Specific shapes (e.g., needles vs. cubes) may be
• Purity: Crystals are often approximately pure solute, required
separating it from impurities in the mother liquor • Uniformity: Consistent size/shape is highly desirable
✓ Minimizing caking during storage/packaging.
✓ Ease of pouring and handling.
✓ Efficient washing (removes mother liquor).
✓ Efficient filtering (solid-liquid separation).
✓ Uniform behavior in downstream uses.

5
Crystal Definition & Structure
Definition:
A crystal is a solid composed of atoms, ions, or molecules arranged in an orderly,
repetitive three-dimensional pattern.

Structure:
Highly organized matter. Constituents are located in arrays called space lattices.

Characterization:
Interatomic distances and angles between lattice planes are measured using
techniques like X-ray diffraction (XRD).

Appearance:
Crystals typically appear as polyhedrons with flat faces and sharp corners/edges.

6
Crystal Geometry & Classification

Constancy of Classification Basis

Interfacial Angles Crystals are classified into
While relative face sizes may systems based on the
vary for crystals of the same arrangement of imaginary
substance, the angles axes used to describe the
between corresponding faces interfacial angles.
are constant and
characteristic of that
material.

Seven Crystal Systems

Defined by the relationships between the lengths of these axes and
the angles between them.

7
The Seven Crystal Systems (Part 1)

Cubic Tetragonal Orthorhombic Hexagonal

Three equal axes, all at right Three axes, all at right angles; Three axes, all at right angles, Four axes; three are equal, lie
angles (90°) to each other. two are equal in length, the all of different lengths. in one plane at 60° to each
(e.g., NaCl) third is different. other; the fourth is
perpendicular to this plane
and of a different length.

8
The Seven Crystal Systems (Part 2)

a≠b≠c

Monoclinic Triclinic Trigonal (Rhombohedral)

Three unequal axes; two are at right Three unequal axes, all at unequal angles Three equal axes, all equally inclined to
angles in a plane, the third is inclined to to each other (not 90°, 60°, or 30°). each other (not 90°).
this plane.

9
Crystal Habit vs. Crystal System
Crystal System Crystal Habit Shape (Needles, Plates)

Fundamental classification based on The external shape or relative Overall shapes relate to habit, not
internal lattice structure and symmetry development of different faces. Habit necessarily the fundamental crystal
(e.g., NaCl is always Cubic). can be influenced by process conditions system, and depend heavily on growth
and impurities. conditions.

Example: Pure NaCl crystallizes with

cubic faces. NaCl crystallized with
certain impurities present can form
octahedral faces.

Both forms are still classified under

the Cubic system.

10
 Module 2:
Physicochemical Principles

11
Equilibrium Solubility
Equilibrium State Solubility Curve
In crystallization, equilibrium is reached when the Represents this equilibrium state. It plots solubility
solution (mother liquor) is saturated with the solute at (concentration of solute in a saturated solution) versus
the system temperature. temperature.

Primary Factor Pressure effect

Temperature is the main variable affecting solubility for Generally negligible for solid solubility in liquids.
most solid-liquid systems.

Data Sources
Chemical handbooks (e.g., Perry's - P1) contain
solubility data and curves.

12
Solubility Curves - Examples
Common Units: Solubility often expressed as (mass of
anhydrous solute) / (100 mass units of solvent), e.g., kg Na₂CO₃ /
100 kg H₂O.

Curve Shapes Vary:

• Sharp Increase with Temp: e.g., KNO₃, KI and NaNO₃.

Often indicates no stable hydrates form.
• Small Change with Temp: e.g., NaCl. Crystallization by
cooling is less effective; evaporation is needed.
• Decrease with Temp: Some substances become less soluble
as temperature increases (e.g., NH₃ and HCl).

13
Solubility Curves - Hydrates
Hydrated Crystals:
Some salts incorporate specific amounts of water into their crystal
structure (water of hydration).

Solubility Curve Breaks:

When different stable hydrate forms exist at different temperatures,
the solubility curve shows distinct breaks or changes in slope at the
transition temperatures.

Example: Sodium Thiosulfate (Na₂S₂O₃):

• Below 48.2°C: Stable solid is Pentahydrate (Na₂S₂O₃·5H₂O)
Interpretation: The curve shows the solubility of the
• 48.2°C - ~65°C: Stable solid is Dihydrate (Na₂S₂O₃·2H₂O)
anhydrous salt, but the solid phase in equilibrium depends on the
• Above ~70°C: Stable solid is Anhydrous (Na₂S₂O₃) temperature range.

14
Yields in Crystallization
Yield Calculation
Yield determines the amount of crystals produced.

Basis (Assuming Equilibrium)

1. Initial concentration of solute in the feed solution
2. Final temperature of the crystallization process
3. Solubility of the solute at the final temperature (obtained from the solubility curve)
4. Amount of solvent evaporated (if any)

Equilibrium Assumption
Assumes the final mother liquor is saturated at the final temperature.

Caveat: If crystal growth is slow (e.g., high viscosity, low crystal surface area), the mother liquor might remain slightly
supersaturated, leading to an actual yield lower than the equilibrium prediction.

15
Material Balances
Anhydrous Crystals Hydrated Crystals

Simple balances: Water balance must account for water removed within the
crystal structure.
• Overall Balance: Feed (F) = Mother Liquor (S) +
Crystals (C) [+Evaporated Solvent (W)] • Overall Balance: F = S + C (+ W)
• Solute Balance: Solute in Feed = Solute in Mother Liquor • Water Balance: Water_in_F = Water_in_S +
+ Solute in Crystals Water_in_C (+ W)
• Solute Balance: Solute_in_F = Solute_in_S +
Solute_in_C
• (Where F=Feed, S=Mother Liquor, C=Crystals,
W=Evaporated Water)

16
Example: Yield Calculation Setup
Problem Statement
A salt solution weighing 10,000 kg with 30 wt% Na₂CO₃ is cooled to 293 K (20°C). The salt crystallizez as the
decahydrate (Na₂CO₃·10H₂O). What will be the yield of the crystals if the solubility at 20 0C is 21.5 kg anhydrous
Na₂CO₃ / 100 kg of total H₂O. Do this for the following cases:
a) No water evaporation.
b) 3% of feed weight evaporated as water.

Solution
Data Mass Fractions
F = 10000 kg. Mass fraction of Na₂CO₃ in feed =
30
=
30
= 0.23077
30+100 130
C = kg crystals.
100 100
S = kg mother liquor. Mass fraction of H2O in feed = = = 0.76923
30+100 130
W = kg water evaporated. 106
Mass fraction of Na₂CO₃ in crystals C = = 0.37037
286.2
Molecular Weights: Mass fraction of H2O in crystals C =
180.2
= 0.62963
286.2
Na₂CO₃ = (23×2)+12+(16×3) = 106. g/mol
21.5 21.5
H₂O = 2 x 1.008 + 16 = 18.02 g/mol Mass fraction Na₂CO₃ in mother liquor S = = = 0.17695
21.5+100 121.5

Na₂CO₃.10H₂O= 286.2 g/mol Mass fraction of H2O in mother liquor S =

100
=
100
= 0.82304
21.5+100 121.5

17
Solution Case (a)
W= 0 kg H2O
Case (a): W = 0 (no evaporation)

Total Mass Balance:

10 000 kg solution Cooler and S kg solution
F=S+C+W (1)
30% Na₂CO₃ Crystallizer 21.5 kg Na₂CO₃ /100 kg total
or 10,000 = S + C + 0 H2O
⇒ C = 10000 – S (2)

C kg crystals Na₂CO₃ ·10H₂O

MgSO4 Balance
Na₂CO₃ in Feed = Na₂CO₃ in Mother Liquor + Na₂CO₃ in Crystals
0.3(1000) = 0.17695 𝑆 + 0.37037𝐶 (3)
Substitute C in equation 3 using equation (2)
3000 = 0.17695 𝑆 + 0.37037 (10000 – S ) (4)
Expand for S in equation (4)
3000 = 0.17695𝑆 +3703.7 – 0.37037𝑆
703.7 = 0.19342S
⇒ S = 703.7/0.19342 = 3638.2 kg S = 3638.2 kg
C = 10,000 - 3638.2 = 6361.8 kg C = 6361.8 kg 18
Solution Case (b) W= 300 kg H2O

Case (b): W = 0.03 * F = 300 kg H₂O evaporated

Total Material Balance 10 000 kg solution Cooler and S kg solution
F=S+C+W 30% Na₂CO₃ Crystallizer 21.5 kg Na₂CO₃ /100 kg total H2O
10,000 = S + C + 300
9700 = S + C
⇒ C = 9700 - S (5)
C kg crystals Na₂CO₃ ·10H₂O
H2O Mass Balance
0.7(10,000) = 0.82304S + 0.62963C + 300
6700 = 0.82304S + 0.62963C (6)

Substitute for C in equation (6) using equation (5)

6700 = 0.82304S + 0.62963(9700 – S)
6700 = 0.82304S + 6107.411 - 0.62963S

S = 3064.42 kg
⇒ C = 6,635.58 kg

19
Heat Effects in Crystallization
Heat of Solution
Heat absorbed or evolved when a solute dissolves.

• Endothermic (Heat Absorbed): If solubility increases with temperature.

• Exothermic (Heat Evolved): If solubility decreases with temperature.
• Zero: If solubility is independent of temperature.

Heat of Crystallization
Heat effect when crystals form from solution. It is the negative of the heat of solution at the same concentration.

Approximation
If the heat of dilution (from saturation to infinite dilution) is small, the heat of crystallization can be approximated as
the negative of the heat of solution at infinite dilution (standard tabulated value). With many materials this heat of
dilution is small compared with the heat of solution, and this is often reasonably accurate.

20
Heat Balances in Crystallizers
Purpose

To determine the amount of heat to be added or removed during the process.

Preferred Method: Enthalpy-Concentration Chart

However, only a few such charts are available, including the following systems: CaCl₂-H₂O,
MgSO₄-H₂O and ferrous sulfate– water.

1. Read enthalpy of feed (H₁) at feed T and concentration.

2. Read enthalpy of final mixture (H₂) (crystals + mother liquor) at final T and overall
concentration.
3. If evaporation occurs, find enthalpy of vapor (Hv) from steam tables.

Total Heat Absorbed: q = (H₂ + Hv) - H₁ (Eq 12.11-4)

• q > 0: Heat must be added (cooling crystallization where heat of soln is absorbed).
• q < 0: Heat must be removed (cooling crystallization where heat of soln is evolved, or
evaporative crystallization).

21
Example: Heat Balance Setup
Problem Statement
A feed solution of 2268 kg at 327.6 K contains 48.2 kg MgSO₄/100 kg total water is cooled to 293.2 K, where
MgSO₄·7H₂O crystals are removed. The solubility of the salt is 35.5 kg/100 kg total water. The average heat
capacity of the feed solution can be assumed as 2.93 kJ/kg·K, The heat of solution at 291.2 K is −13.31×103
kJ/kg mol MgSO₄·7H₂O. Assuming no water is vaporized, calculate:

i. Yield of MgSO₄·7H₂O crystals.

ii. Make a heat balance to determine the total heat absorbed, q,

Note: use the following molecular weight values:

Mg = 24.305 g/mol, S = 32.065 g/mol, O = 16 g/mol H = 1.008 g/mol

Solution
Data Molecular Weights: Mass Fractions :
F = 2268 kg. MgSO4 = 24.305 + 32.065 + 64 = 120.37 g/mol Mass fraction of MgSO4 in feed =
48.2
=
48.2
= 𝟎. 𝟑𝟐𝟓𝟐𝟒
H2O = 2 x 1.008 + 16 = 18.016 g/mol 48.2+100 148.2
C = kg crystals 100 100
MgSO4.7H2O = 120.37 + 7(18.016 ) = 246.482 g/mol Mass fraction of H2O in feed = = = 𝟎. 𝟔𝟕𝟒𝟖
S = kg mother liquor. 48.2+100 148.2
120.37
W = kg water evaporated Mass fraction of MgSO4 in crystals C = = 𝟎. 𝟒𝟖𝟖𝟑𝟓𝟖
246.482
. 126.112
Mass fraction of H2O in crystals C = = 𝟎. 𝟓𝟏𝟏𝟔𝟒
246.482
. 35.5 35
Mass fraction MgSO4 in mother liquor S = = = 𝟎. 𝟐𝟔𝟏𝟗𝟗𝟐
35.5+100 135.5
35.5 100
Mass fraction of H2O in mother liquor S =
35.5+100
=
135.5
= 𝟎. 𝟕𝟑𝟖 22
Solution
(i) Yield of MgSO₄·7H₂O crystals
W kg H2O
Total Mass Balance:
F=C+S (1)
or 2268 = C + S
2268 kg solution Cooler and S kg solution
⇒ S = 2260 – C (2) 48.2% MgSO₄ /100 kg total H2O Crystallizer 35.5 kg MgSO₄/100 kg total H2O

MgSO4 Balance
0.32524(2268) = 0.488358C + 0.261992S (3) C kg crystals MgSO₄·7H₂O
Substitute S in equation (3) using equation (2)
737.64 = 0.488358C + 0.261992 (2268 – C) (4)
Expand for C in equation (4)
737.636 = 0.488358C +594 – 0.261992C
143.636 = 0.226366C
143.636
𝐶= = 634.1 kg
0.226366
Solve for S:
S = 2268 – 634.1 = 1633.9 kg
S = 1633.9 kg
C = 634.1 kg 23
Solution
(ii) Make a heat balance to determine the total heat absorbed, q,

To make the heat balance a datum of 293.2 K will be used .

The enthalpy of the feed (H1) is given as:
H1 = mcpΔT (1)
Where, m = 2268 kg, cp = 2.93kJ/kg.k, and ΔT = T2 – T1
H1 =2268(293.2–327.6 )(2.93) = –228,600 kJ

The heat of Crystallization (ΔHcrystallization) is given as:

ΔHcrystallization = – Heat of solution/mass of crystals = –(–13.31 x 103)/246.482 = 54 kJ/kg crystals
⇒ Total of heat of crystallization = 54 x 634.1 = 34,241.4 kJ
Therefore, the total heat absorbed, q, is
q = H1 – Heat of crystallization = – 228600 – 34241.4 = –262841.4 kJ.

Since q is negative, heat is given off and must be removed

24
 Module 3:
Crystallization Equipment

25
Introduction to Crystallizers
Operation Mode
Classified as Batch or Continuous (continuous generally preferred for large scale).

Primary Function
To create a supersaturated solution, which is the driving force for both nucleation and crystal growth.
Crystallization cannot occur without supersaturation.

Classification Methods Based on:

1) Method used to achieve supersaturation.

2) Method used to suspend growing crystals.

3) How supersaturated liquid contacts crystals.

26
Classification by Supersaturation Method

Cooling Evaporation Adiabatic

Evaporation/Cooling
Solution cooled below saturation Solvent is evaporated, increasing solute
(Vacuum)
temperature (with negligible concentration above saturation (with
evaporation). Requires solubility to little or no cooling). Used when Hot, saturated feed enters a vacuum
decrease significantly with solubility changes little with chamber. Solvent flashes (evaporates),
temperature. Most common method. temperature (e.g., NaCl). (e.g., cooling the solution adiabatically.
(e.g., Tank crystallizers). Evaporator-crystallizers). Combines evaporation and cooling
effects. Very important for large-scale
production. (e.g., Vacuum
crystallizers).

27
Classification by Suspension & Contact Method
Suspension Method Liquid-Crystal Contact Method

How crystals are kept moving/prevented from settling. • Circulating Magma: The entire slurry (magma = crystals +
liquid) is circulated through zones of supersaturation generation
• Agitated Tank
and crystal growth. Supersaturation and growth occur
• Circulation through a heat exchanger (external cooling/heating) simultaneously in the presence of all crystals.
• Scraped Surface heat exchanger (prevents fouling) • Circulating Liquid (or Classified Suspension):
Supersaturated liquid is generated separately and then passed
through a (often fluidized) bed of classified crystals where growth
occurs. Saturated liquid is recycled. Allows better control over
crystal size.

28
Tank Crystallizers
Description:
Oldest method, simple, often batch. Hot saturated solution cooled naturally in open
tanks. Mother liquor drained, crystals manually removed.

Characteristics:
• Poor control over nucleation and crystal size.
• Significant inclusion of mother liquor in crystals (lower purity).
• High labor costs

Modifications:
Cooling coils or jacket can be added, along with an agitator, to improve heat transfer
and suspension.

Drawbacks:
Crystal buildup (encrustation) on cooling surfaces is problematic.

Applications:
Limited use today, sometimes for specialized fine chemicals or pharmaceuticals.

29
Scraped Surface Crystallizers - Swenson-
Walker
Purpose: To handle solutions where crystal buildup on
cooling surfaces is severe.

Swenson-Walker Type

• Consists of an open trough (≈ 0.6 m wide) with a rounded

bottom and an external cooling jacket.
• A slow-speed (few rpm) spiral agitator rotates inside.
Characteristics: Generally produces a wide crystal size
• The agitator blades pass close to the cooled wall, breaking
distribution. Continuous operation possible by connecting
off any deposited crystals and keeping the crystals
units in series.
suspended.

30
Scraped Surface Crystallizers - Double-Pipe
Double-Pipe Type (Votator)

• Similar to a double-pipe heat exchanger. Cooling medium

flows in the annulus.
• Process solution/slurry flows through the inner pipe.
• An internal agitator shaft is fitted with spring-loaded
scraper blades that wipe the inner surface of the inner pipe.

Characteristics:
Provides good heat transfer coefficients due to scraping action.
Often used for viscous materials or where solids deposit easily. Applications: Crystallizing ice cream, plasticizing margarine.

31
Circulating Liquid Evaporator-Crystallizer
(Oslo / Krystal)
Type
• Combination Evaporator-Crystallizer (Supersaturation via Evaporation).
• Circulating Liquid Contact Method.

Operation
1. Clear saturated liquid drawn from above crystal bed is pumped (often screw pump)
through a heater.

2. Heated liquid flashes in the vapor space above the main body,
generating supersaturation by evaporation. Vapor is condensed.

3. Supersaturated liquid flows down a central pipe (downcomer).

4. Liquid flows upwards through a fluidized/agitated bed of growing

crystals. Supersaturation is released as growth on existing crystals.

5. Clear saturated liquid overflows and recycles to the heater (mixed with feed).

6. Larger crystals settle to the bottom and are withdrawn as product slurry.

32
Circulating Magma Vacuum Crystallizer
Type: Adiabatic Evaporation/Cooling (Vacuum). Circulating Magma Contact
Method.

Operation

1. Magma (slurry of crystals and liquid) is drawn from the main body by a
circulating pump (e.g., screw pump).
2. Magma flows through an external heater; temperature is raised slightly (2-
6 K). No boiling occurs in the heater.
3. Heated magma returns to the crystallizer body, mixing with the bulk slurry
near the surface.
4. The vessel is under vacuum (e.g., via steam jet ejector). The heated liquid
boils/flashes at the surface, causing adiabatic cooling and generating
supersaturation.
5. Supersaturation is relieved by growth onto the suspended crystals
circulating within the magma.
6. Vapors leave through the top. Product slurry is withdrawn from the
circulation loop or body.

33
 Module 4:
Crystallization Theory

34
Introduction to Theory: Nucleation & Growth
Overall Process:
Crystallization involves two fundamental, sequential (and sometimes simultaneous) steps:

1. Nucleation: Formation of new, tiny solid entities (nuclei) from the supersaturated solution. These nuclei must reach
a critical size to be stable.
2. Crystal Growth: Subsequent increase in size of the stable nuclei or existing crystals by deposition of solute
molecules from the supersaturated solution.

Driving Force:
Supersaturation is essential for both nucleation and growth. Neither step occurs in saturated or undersaturated
solutions.

Starting Conditions:
If the solution is initially free of crystals (or seed crystals), nucleation must occur first before growth can begin.

35
Nucleation: Effect of Crystal Size on Solubility
Thermodynamic Effect

Very small crystals (sub-micron) have a significant surface energy relative to their bulk energy.

Result

Small crystals have a higher solubility than larger crystals of the same material at the same temperature.

Implication (Ostwald Ripening)

In a solution that is supersaturated with respect to large crystals but only just saturated (or undersaturated) with respect to very
small crystals, the large crystals will grow while the small ones dissolve.

Relevance:

This difference in solubility is a key factor influencing the stability of initial clusters formed during nucleation.

36
Nucleation Mechanisms: Homogeneous
Nucleation
Mechanism Conditions

Arises from random fluctuations in concentration within a Requires high supersaturation and minimal agitation.
perfectly clear solution (no foreign particles). Molecules collide
Industrial Relevance
and form temporary clusters (aggregates).
Believed to be less important in typical commercial
Stability
crystallizers, where supersaturation is usually kept low and
If supersaturation is sufficiently high, a cluster may randomly agitation is present.
reach a critical size and structure (oriented lattice) to become a
stable nucleus capable of further growth.

37
Nucleation Mechanisms: Contact Nucleation
(Secondary Nucleation)
Key Factor
Definition Agitation intensity strongly influences the rate of contact nucleation.
Nucleation induced by the presence of existing crystals of the
solute. Dominant mechanism in most industrial crystallizers.

Two Types
1. Crystal-Surface Contact: Nuclei formed due to
interactions between growing crystals and external surfaces
(crystallizer walls, agitator blades). Mechanisms involve
disrupting pre-ordered solute clusters near the crystal face or
micro-abrasion/breakage of fragile growths on the crystal
surface.
2. Crystal-Crystal Contact: Nuclei generated by collisions
between existing crystals in the agitated magma.

38
Nucleation in Commercial Crystallizers
Typical Conditions Dominant Mechanism Design Implication
Low levels of supersaturation Contact Nucleation is the Predicting nucleation rates is
(optimal for uniform growth) and primary source of new crystals difficult theoretically. Design often
sufficient agitation (to suspend under these conditions. relies on experimental data from
crystals, enhance heat/mass Homogeneous nucleation is largely the specific crystallizer or
transfer). absent. correlations developed from
contact nucleation studies.

39
Crystal Growth Rate: Introduction
Definition Resistances in Series

Rate at which a crystal increases in size. Often measured as the The overall growth rate is limited by the combined resistance of
distance a crystal face moves perpendicular to itself per unit these two steps:
time.
• Mass Transfer (Diffusion) Resistance.
Mechanism • Surface Integration (Surface Reaction) Resistance.

A layer-by-layer deposition process occurring only on the outer Driving Force Supersaturation (difference between bulk
crystal faces. concentration and saturation concentration) drives both steps.

Requirements

1. Solute must be transported from the bulk solution to the

crystal face.
2. Solute molecules must be integrated into the crystal lattice
at the surface.

40
Crystal Growth: Mass Transfer Step
Process

Diffusion of solute molecules from the bulk solution (concentration yA, mole fraction) through the boundary layer surrounding the
crystal to the crystal surface (concentration y'A).

Rate Equation

• NA / Ai = ky* (yA — y'A)

• Where:
• NA : Molar rate of solute transfer (kg mol A/s)
• Ai : Surface area of crystal face i (m²)
• ky : Mass transfer coefficient (kg mol / s·m²·mole frac)
• (yA — y’A) : Concentration driving force across the boundary layer

The mass transfer coefficient (ky) can be estimated using correlations from fluid dynamics and mass transfer theory.

41
Crystal Growth: Surface Integration Step
Process

Incorporation of solute molecules arriving at the surface (y'A) into the fixed crystal lattice structure. This is akin to a surface reaction
occurring at a finite rate.

Rate Equation

• NA / Ai = ks* (y’A — yAe)

• Where:
• ks : Surface integration (or surface reaction) coefficient (kg mol / s·m²·mole frac). Reflects the ease/speed of lattice
incorporation.
• yAe : Solute mole fraction at saturation (equilibrium concentration at the crystal surface).
• (y’A — yAe): Concentration driving force for the surface integration step.

42
Crystal Growth: Overall Growth Rate
Combined Resistance Rate Control

The overall growth rate depends on the total driving force (yA - • If ky is very large (fast diffusion), 1/ ky ≈ 0, then K ≈ ks.
yAe) and the combined resistances (1/ky + 1/ks). Growth is surface-integration controlled.
• If ks is very large (fast integration), 1/ ks ≈ 0, then K ≈ ky.
Overall Rate Equation
Growth is diffusion controlled.
By eliminating the intermediate surface concentration y'A:
Challenges:
• NA / Ai = K* (yA — yAe)
Predicting K or ks values is difficult for commercial crystallizers
• Where K is the Overall Mass Transfer (Growth)
due to complex flow patterns and varying local supersaturation.
Coefficient, defined by:
Experimental data is often required.
• 1 / K = 1 / ky + 1 / ks

43
Crystal Growth: McCabe's ΔL Law
Statement (McCabe, M1) Implication

All geometrically similar crystals of the same material, when If this law holds, the difference in size between any two crystals
growing in the same solution (same temperature, remains constant as they grow. It simplifies the analysis of
supersaturation, environment), tend to grow at the same crystal size distributions (CSD) in crystallizers. Assumes growth
linear rate. rate is independent of crystal size (for sizes typically
encountered).
Linear Growth Rate

Measured as the increase in a characteristic linear dimension

(ΔL), such as diameter or edge length, per unit time (dL/dt).

44
Crystallization Equipment Selection Guide
Crystallizer Type Best for Limitations

Tank Crystallizer Small batches, specialty chemicals Poor size control, encrustation

Swenson-Walker Solutions prone to encrustation Wide size distribution

Double-Pipe (Votator) Viscous materials, food products Limited capacity

Oslo/Krystal When uniform crystal size is critical More complex operation

Vacuum Crystallizer Large-scale production, heat-sensitive Higher capital cost

materials

45
Crystallization Process Variables

3 5-15°C 2-5%
Key Process Variables Typical Cooling Range Supersaturation Level
Temperature, concentration, and Optimal temperature difference for Typical supersaturation maintained in
agitation are the three primary variables controlled cooling crystallization industrial crystallizers
that control crystallization

46
Troubleshooting Common Crystallization
Issues

Excessive Nucleation Encrustation Poor Crystal Habit Insufficient Yield

Caused by high Crystal buildup on cooling Irregular or undesired crystal Lower than expected crystal
supersaturation, excessive surfaces and walls. Reduces shapes. Often caused by recovery. May be due to
agitation, or impurities. heat transfer efficiency. impurities or rapid growth. incomplete cooling, solubility
Results in small, numerous Solution: Use scraped surface Solution: Control growth rate, data errors, or mother liquor
crystals. Solution: Reduce equipment, optimize flow filter feed solution, add habit retention. Solution: Verify
cooling rate, optimize patterns, periodic cleaning. modifiers if appropriate. solubility data, extend cooling
agitation, use seed crystals. time, improve solid-liquid
separation.

47
Summary of Key Concepts
Product Quality
Crystal yield, purity, size, shape, and uniformity

Process Understanding
Solubility curves, material balances, heat effects

Equipment Selection
3 Tank, Scraped Surface, Oslo, Circulating Magma

Theoretical Foundation
Nucleation, Growth, McCabe's ΔL Law

Fundamental Principle
Supersaturation drives all crystallization

48
Fundamentals of Crystal Formation

Crystal Growth: Building the

Nucleation: Birth of Seed Structure
Supersaturation: The Driving Crystals
Once viable nuclei form, crystal growth
Force
The first phase of crystallization involves begins as additional molecules migrate
Crystallization requires a thermodynamic nucleation—the formation of tiny seed from the solution to the crystal surface.
driving force to initiate. This typically crystals that serve as templates for The rate of this growth and the balance
comes from supersaturation—a state further growth. These initial nuclei must between nucleation and growth
where the solution contains more reach a critical size to become stable and determine the final crystal size
dissolved solute than it can maintain in prevent redissolution. distribution.
equilibrium. This unstable state provides
the energy needed for crystal formation.
Nucleation Mechanisms
Homogeneous Nucleation Heterogeneous Nucleation

Occurs spontaneously within the bulk solution without any Takes place on pre-existing surfaces such as vessel walls,
solid surfaces to facilitate the process. This mechanism requires impurities, or deliberately added seed crystals. The energy
significantly higher supersaturation levels to overcome the barrier is substantially lower since the surface provides a
substantial energy barrier of forming a completely new template that facilitates the ordering of molecules.
interface.
This mechanism dominates industrial processes, where seeding
In practice, true homogeneous nucleation is rare in industrial is commonly employed to control crystallization at manageable
settings due to the extreme conditions required to initiate it. supersaturation levels.
Crystal Growth Mechanisms
Diffusion to Surface Surface Integration
Solute molecules must travel through the Once at the surface, molecules must orient
solution to reach the crystal surface. The correctly and integrate into the crystal
concentration gradient between the bulk lattice. This step often determines the
solution and the crystal interface drives this overall growth rate for many crystallization
movement. processes.

Solution Flow Heat Release

Agitation affects both diffusion and surface Crystal formation releases latent heat that
integration by influencing concentration must be removed to maintain
gradients and preventing stagnant supersaturation. Efficient heat transfer is
boundary layers around growing crystals. critical for sustained crystallization.
Crystallization Thermodynamics
Equilibrium
At saturation point, dissolved and solid phases exist in balance

Supersaturation
Creates thermodynamic driving force for crystallization

Energy Barrier
Must be overcome for stable nuclei to form

Exothermic Process
Releases heat that must be removed to maintain conditions

Crystallization occurs when a thermodynamically favorable transition from solution to solid crystal reduces the system's free energy. The process
involves overcoming an initial energy barrier for nucleation, after which crystal growth becomes energetically favorable. The exothermic nature of
crystallization means that careful heat management is essential for maintaining supersaturation throughout the process.