CRYSLLISATION

CRYSLLISATI
ON
 2 Presented By:

 Mubashir Zawar 2K20-ChE-14

 M. Usman Ali 2K20-ChE-29

 Abu Bakar Asim 2K20-ChE-121

 Saad Diyan 2K20-ChE-211

 Muhammad Sameer 2K20-ChE-11

 Abdul Muqeet Zahid 2K20-ChE-116

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Crystallisation
 3 Table of Content
Introduction

Methods

Crystallisation from Solution

Crystallisation from Melts

Comparison of Batch vs. Continuous

Crystallisation

Selection of Crystalliser

Challenges and their Solution

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Crystallisation
 4 Crystallisation
 Crystallisation is the physical transformation (phase transition) of a liquid,
solution, or gas to a crystal, which is a solid with an ordered internal
arrangement of molecules, ions, or atoms

 Examples:

1. Salt production

2. Sugar crystallization

3. Purification of chemicals (removing impurities from salt obtained from seawater)

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Crystallisation
 5 Importance in Engineering:
 Used in industries like chemical engineering, pharmaceuticals, food processing and
materials engineering

 Many organic liquids are purified by crystallisation rather than by distillation,

enthalpies of crystallisation are generally much lower than enthalpies of
vaporisation and crystallisation may be carried out closer to ambient temperature
thereby reducing energy requirements. Against this, crystallisation is rarely the
last stage in a process and solvent separation, washing and drying stages are
usually required.

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Crystallisation
 6
Caking of Crystals
Crystalline materials tend to cake or cement together during storage due to factors
such as crystal size, shape, moisture content, and storage conditions.

To minimize caking:

 Ensure efficient drying

 Use airtight packaging

 Avoid compaction during storage

 Apply inert dust coatings as moisture barriers

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Crystallisation
 7 Methods of Crystallisation

Crystallisation from Solutions

Crystallisation from Melts

Crystallisation from Vapours

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Crystallisation
 8 Crystallisation from Solutions:

COOLING EVAPORATIVE REACTION

CRYSTALLISATI CRYSTALLISATI CRYSTALLISATI
ON ON ON
(reducing temperature) (removing solvent) (by chemical reaction)

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Crystallisation
 9 Cooling Crystallisation:
 Cooling Crystallisation is a method of Crystallisation where crystals are formed by
reducing the temperature of a solution, causing the solute to become less soluble
and precipitate as solid crystals.

 Process:

• A hot, saturated solution is cooled under controlled conditions.

• Cooling causes supersaturation, which is the driving force for crystallization.

• Nucleation occurs first, followed by crystal growth.

Example:

Production of salts, sugar, Fertilizers

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 10 Cooling Crystalliser:
The principle of cooling
crystallisation is based on the
temperature-solubility
relationship of a solute in a
solvent. By cooling a
saturated solution, the
solubility of the solute
decreases, causing the
solution to become
supersaturated.

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 11 Evaporative Crystallisation
 Evaporative Crystallisation is a process where crystals are formed by removing solvent
through evaporation, leading to supersaturation and subsequent crystal formation.

 Process

• Heating the Solution: The solution is heated to facilitate solvent evaporation.

• Supersaturation: As the solvent evaporates, the solute concentration increases, creating a

supersaturated state.
• Nucleation and Growth:
• Nuclei (tiny crystal "seeds") form, and solute particles deposit Examples:
onto these seeds. Production of common salt (NaCl)
• Crystal growth occurs until equilibrium is reached. from seawater.
•Crystallisation of sugars, fertilizers
• Separation: Crystals are separated from the remaining
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 12 Reaction Crystallisation
 Reaction Crystallisation is a process where crystals are formed as a result of a chemical
reaction that produces a sparingly soluble compound, leading to its precipitation as crystals.

 Process

 Mixing of Reactants: Two or more solutions are mixed under controlled conditions.

 Chemical Reaction: A reaction occurs, forming a product with low solubility in the solution.

 Supersaturation: The concentration of the product exceeds its solubility limit, leading to
supersaturation.

 Nucleation and Growth: Crystals form and grow as the product precipitates out of the solution.

 Separation: The crystals are separated from the reaction mixture using filtration, centrifugation, or
drying.

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13
 Examples:

Water Treatment: Removal of contaminants by precipitation (e.g.,

lime softening).

Pharmaceutical Industry: Synthesis and Crystallisation of drug

intermediates.

Metal Recovery: Precipitation of metals as hydroxides, sulfates, or

carbonates.

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14 Cooling Crystalliser

 A cooling crystalliser is a type of crystallizer used to produce crystals by

reducing the temperature of a supersaturated solution. This process
takes advantage of the fact that solubility decreases as the temperature
decreases, leading to the precipitation of crystals from the solution. It is one
of the simplest and most widely used methods for crystallisation.

 The principle of cooling crystallisation is based on the temperature-

solubility relationship of a solute in a solvent. By cooling a saturated
solution, the solubility of the solute decreases, causing the solution to
become supersaturated.

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 15 CRYSTALLISATION FROM MELTS
 A melt is a liquid or a liquid mixture at a temperature near its freezing point and melt
crystallisation is the process of separating the components of a liquid mixture by cooling until
crystallised solid is deposited from the liquid phase.

Two Basic Techniques of Melt Crystallisation:

 Gradual Deposition:

• Crystals form progressively on chilled surfaces in a static or laminar-flow melt.

• Example: Rotary Drum Crystalliser – A rotating horizontal drum partially immersed in the melt.
Crystalline layers form on the drum’s surface and are scraped off.

 Fast Generation of Discrete Crystals:

• Crystals form quickly in the body of an agitated vessel.

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16 Drum Crystallisers

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 17 Comparison of Batch vs. Continuous Crystallization
Aspect Batch Crystallization Continuous Crystallization
Operates continuously with a constant
Operation Mode Operates in discrete cycles (batch-wise)
feed and discharge
Product More consistent product quality over
Possible variation in product from batch to batch
Consistency time
Highly flexible for adjusting
Flexibility Less flexible, especially for changes in parameters temperature, supersaturation, and
other factors
Better control over temperature,
Limited control over temperature, supersaturation,
Control supersaturation, nucleation, and crystal
and nucleation
growth
Can produce high-purity crystals, but may involve May have issues with product purity
Purity & Quality
higher operating costs and consistency without proper control
Easier to control size distribution but
Crystal Size May produce a wide range of crystal sizes; specific
may require a holding tank for
Distribution conditions can be maintained
equilibrium
More complex and expensive
Simpler equipment, ideal for small-scale or high- equipment due to the need for
Equipment
purity applications continuous flow, heat exchange, and
Crystallisation control
More energy-efficient in continuous
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May be less energy-efficient due to intermittent
Energy Efficiency operation, but may need more energy
operations
Crystallisation to maintain conditions
 18 Comparison of Batch vs. Continuous Crystallization
Cleaning and maintenance are more
Cleaning and Easier to clean between batches, reducing cross- challenging due to continuous
Contamination contamination risks operation, leading to potential
contamination if not properly managed

Lower operating costs due to higher

Operational Higher operating costs due to lower throughput throughput, but can incur maintenance
Costs and potential for variation and washout costs due to self-seeding
or fouling

Suitable for small to medium-scale production or Ideal for large-scale, steady production
Scale
specialized products needs

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 19
Case Study Purification of Sodium Chloride
 (NaCl)
The industrial production of purified NaCl primarily relies on Crystallisation
processes to remove impurities like calcium sulfate (CaSO₄), magnesium chloride
(MgCl₂), and other soluble or insoluble contaminants.

 Raw Salt Sources

Sea Water (Solar Salt): Salt obtained by evaporation of seawater.
Rock Salt: Mined from underground deposits.
Brine: Saline water from natural or artificial brine wells.

Raw Salt → Dissolution → Chemical Treatment → Evaporative Crystallisation →

Crystal Washing → Drying → Pure NaCl

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 20 Steps in Purification of Sodium Chloride

1. Raw Salt Dissolution

 The raw salt is dissolved in water to form a saturated brine solution.

 Insoluble impurities like sand, clay, and organic matter remain suspended or settle out and are
removed via filtration or sedimentation.

2. Chemical Treatment of Brine

 To remove soluble impurities such as calcium and magnesium salts, chemical reagents are added:

Lime (CaO) or Sodium Carbonate (Na₂CO₃): Precipitates calcium as insoluble calcium

carbonate (CaCO₃).

Soda Ash: Neutralizes magnesium salts by precipitating magnesium hydroxide (Mg(OH)₂).

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The precipitates (CaCO₃ and Mg(OH)₂) are removed via settling tanks and filtration.
 3. Crystallization
 21 purified brine undergoes evaporative Crystallisation to form NaCl crystals.
The
Process Overview:
 The brine is heated in large evaporators under vacuum to lower the boiling point and reduce
energy consumption.
 Water evaporates, increasing supersaturation and causing NaCl to crystallize.
 Crystals of NaCl precipitate out, while remaining impurities stay in the mother liquor.

4. Separation and Washing of Crystals

 The NaCl crystals are separated from the mother liquor using centrifugation or filtration.
 Crystals are washed with saturated brine to further remove any adhering impurities.
 Water washing is avoided as it may dissolve the crystals.

5. Drying
 The washed NaCl crystals are dried in rotary dryers or fluidized bed dryers to remove residual
moisture. 12/19/2024

 This step ensures a dry, free-flowing final product suitable for packaging.
Crystallisation
22 Selection of Crystalliser
 Analyze the solubility of the solute in the solvent with respect to temperature.

 Identify the required shape, size, and size distribution of crystals.

 Based on the solubility behavior and product requirements

 Compare the costs for installation and operation

 Evaluate Space Availability

 Consider Feed Liquor Characteristics

 Address Mixing and Supersaturation Control

 Finalize the Design

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 23 Challenges in Crystallisation

 Controlling nucleation and crystal size:

Crystal growth may be inconsistent, affecting product quality.

 Impurities in crystallized products

•Impurities can be trapped in crystals or adsorbed on their surfaces, reducing purity.
•Impurities affect crystal growth rates and morphology.

 Scaling issues in industrial equipment

•Scaling (solid deposition) on cooling surfaces and pipes reduces heat transfer efficiency and process
reliability.
•Heavy fouling can lead to production downtime.

 Energy efficiency and optimization

•Crystallisation can be energy-intensive, especially evaporative Crystallisation processes. 12/19/2024

•Energy loss through inefficient cooling or heating systems increases operational costs.
Crystallisation
24 Solutions of Challenges

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 25 REFERENCES
 "Chemical Engineering Volume 2: Particle Technology and
Separation Processes" by Coulson & Richardson

 "Unit Operations of Chemical Engineering" by McCabe, Smith, and

Harriott

 "Handbook of Industrial Crystallization" by Allan Myerson

 Perry's Chemical Engineering Handbook 9th Edition

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Crystallisation
Thank you