Separation Process (Assignment)

Liquid-Liquid Extraction

Figure:
Introduction:
Liquid-liquid extraction (LLE), also called solvent extraction, is a technique
used to separate compounds based on their relative solubilities in two different
immiscible liquids—usually water and an organic solvent. The core idea is to
transfer a solute from one liquid into another, where it is more soluble.

For example, suppose you have a solution of acetic acid in water and you want to
separate the acid. You could use an organic solvent like ethyl acetate that can
selectively pull acetic acid out of the aqueous phase and into the organic phase.

This process is widely used in chemical, pharmaceutical, petrochemical, and

metallurgical industries to separate valuable components from mixtures.

To carry out this extraction efficiently, a variety of specialized equipment is used.

These are designed to ensure proper contact between the two liquid phases,
promote mass transfer, and enable easy separation after extraction. The selection of
equipment depends on several factors such as the properties of the liquids (e.g.,
density difference, interfacial tension), throughput, efficiency requirements, and
operational conditions.

Common types of liquid-liquid extraction equipment include:

 Mixer-settlers
 Centrifugal extractors
 Packed columns
 Spray columns
 Pulsed columns
 Rotating disc contactors (RDCs)
 Scheibel columns

Historical Context:
LLE has been used since the early 20th century in industries like
pharmaceuticals and oil refining. Over time, the process has evolved with
advanced equipment, better solvent selection methods, and automation.
Why Use LLE?
 Low-temperature separation:
 Suitable for heat-sensitive compounds.

 Selective separation:
 It can separate chemically similar compounds.

 Energy efficient:
 Uses less energy than distillation in certain cases.

Working Principle of Liquid-Liquid Extraction Equipment

Liquid-liquid extraction (LLE) is based on the principle of distribution of
a solute between two immiscible or partially miscible liquid phases — typically, an
aqueous phase and an organic solvent. The solute preferentially dissolves in one of
the liquids depending on its solubility and the distribution coefficient.

The driving force for extraction is the difference in chemical potential (or
concentration gradient) of the solute between the two phases.

Steps Involved in the Extraction Process

1. Contact of Phases (Mixing):

The feed liquid (usually containing the solute to be extracted) and

the solvent are brought into intimate contact.

Equipment such as mixers, rotating discs, or packing materials help

disperse one phase into the other to form droplets, increasing the
interfacial area for mass transfer.
 2. Mass Transfer
o The solute begins to move (transfer) from the feed phase to the
solvent phase due to the concentration difference.
o This transfer continues until equilibrium is reached, where the ratio
of solute concentrations in each phase becomes constant (defined by
the distribution coefficient).
o
3. Phase Separation (Settling)

o After the extraction step, the two liquid phases need to be

separated.
o Gravity settlers, centrifugal force, or static settling zones in the
equipment allow the two immiscible liquids to separate based on
their density difference.

4. Recovery
o The extract phase (rich in solute) and the raffinate phase (depleted
in solute) are withdrawn from the equipment.
o Further steps like solvent recovery or back-extraction may follow.

🛠️How This Works in Different Equipment

 Mixer-Settlers:
 Mixing is done in an agitated tank, and separation in a quiet settling
tank.
 Centrifugal Extractors:
 Both mixing and phase separation are done rapidly using centrifugal
force.
 Packed/Spray Columns:
 Phases flow counter-currently; mass transfer occurs as droplets
rise/fall through the continuous phase.

 Rotating Disc/Scheibel Columns:
 Mechanical mixing is enhanced by rotating elements, and separation occurs
in the same unit.

🔍 Important Factors Affecting Working

 Interfacial area:

More surface area = better mass transfer.

 Contact time:

Longer contact = more complete extraction (up to equilibrium).

 Phase ratio:
 Volume ratio of solvent to feed affects extraction efficiency.
 Density difference:
 Affects how easily the phases separate.
 Viscosity:
 High viscosity reduces mass transfer and slows separation.

Liquid-liquid extraction equipment works by efficiently mixing two immiscible

liquids to allow the transfer of a solute from one liquid to another, followed by
their separation into distinct phases. The design and operation of the equipment
aim to maximize mass transfer and minimize phase separation time.

Working Limits of Liquid-Liquid Extraction Equipment

The working limits refer to the physical, chemical, and operational constraints
beyond which the extraction equipment may not function efficiently or safely.
Exceeding these limits can lead to poor phase separation, low extraction
efficiency, equipment damage, or operational instability.
1. Flow Rate Limits

 Minimum Flow Rate:

If the flow rate of either phase is too low, proper mixing may not occur,
resulting in insufficient mass transfer.

In packed or spray columns, low flow can lead to channeling or poor

contact.

 Maximum Flow Rate:

Too high a flow rate may cause flooding in columns or excessive

turbulence in settlers.

High velocity can reduce the residence time needed for separation an
may lead to emulsification.

2. Phase Ratio Limits (Solvent-to-Feed Ratio)

 There is an optimum phase ratio for maximum extraction efficiency.

 Too little solvent leads to incomplete extraction.

 Excessive solvent use increases cost and requires larger downstream

recovery systems.

3. Density Difference Limits

Efficient phase separation relies on a sufficient density difference
between the two liquids.
  If the density difference is very small, settling becomes slow and may
require longer residence time or special equipment like centrifugal
extractors.
 Below a certain density difference, gravity-based separation is
ineffective.

💧 4. Interfacial Tension Limits

 If interfacial tension is too low:

o Leads to stable emulsions, difficult to separate.
o Droplets become very small and don’t coalesce easily.
 Too high interfacial tension:
o Reduces the formation of small droplets, thus decreasing interfacial
area and extraction efficiency.

🧯 5. Temperature Limits

 Each equipment has a temperature range based on materials of construction

and the thermal stability of the liquids.
 Very high temperatures:
o May damage equipment, especially plastic packings or seals.
o Increase volatility of solvents, raising safety concerns.
 Very low temperatures:
o Increase viscosity, reducing mass transfer.
o May cause crystallization or phase freezing.

🧫 6. Viscosity Limits

 High-viscosity fluids:
o Reduce the mobility of the droplets.
o Slow down mass transfer and settling rates.
 Equipment like packed or spray columns struggle with very viscous liquids
unless modified or pulsed.
⚠️7. Emulsion-Forming Tendency

 Some systems naturally form emulsions that are difficult to break.

 Equipment working limits may be exceeded if emulsions persist:
o Settlers may not separate phases.
o Centrifugal extractors may clog.

🔄 8. Mechanical and Structural Limits

 Each piece of equipment has limits on:

o Rotational speed: (for centrifugal or rotating disc contactors)
o Pressure:(particularly in closed systems)
o Pulsation frequency and amplitude:
o (in pulsed columns)

Exceeding these may cause mechanical failure or unsafe operation.

Summary Table:

Parameter Lower Limit Effect Upper Limit Effect

Flow rate poor mixing Flooding, Emulsification

Density difference slow settling -
Interfacial Tension Emulsion formation Poor droplet formation
Temperature Increased viscosity, Volatility, material
crystallization degradation
Viscosity Poor mass transfer Difficult droplet motion,
slow separation
Solvent-to-Feed Ratio Solvent-to-Feed Ratio Economic inefficiency
 Applications of Liquid-Liquid Extraction
1. Chemical Industry
 Separation of organic compounds:

o Aromatic hydrocarbons (e.g., benzene, toluene) from paraffinic
mixtures.
o Acetic acid from aqueous streams using solvents like ethyl acetate.
 Recovery of acids and bases:
 Extraction of hydrochloric, sulfuric, or nitric acids from industrial
waste streams.
 Removal of amines or phenols from wastewater.

 Purification of reaction products:

Removing unreacted reactants or by-products using selective solvents .

2. Pharmaceutical Industry
 Purification of active pharmaceutical
ingredients (APIs):

o Separating APIs from fermentation broths or synthesis mixtures.
o
 Solvent extraction in antibiotic production:
o E.g., penicillin extraction from aqueous broth using butyl acetate or
amyl acetate.
o
 Natural product extraction:

o Isolating alkaloids, essential oils, and plant extracts using organic
solvents.
 3.Petrochemical Industry
 Aromatic/aliphatic hydrocarbon separation:

o Sulfolane extraction process for BTX recovery (benzene, toluene,
xylene).

Desulfurization:Removing sulfur-containing compounds from diesel

or other fuels.

 Lubricant purification

Extraction of undesirable components to improve oil quality.

4. Hydrometallurgy & Metallurgical Industry

 Recovery of valuable metals:

 from ores and solutions:
o Uranium, copper, nickel, cobalt, and zinc extraction.
o Use of organophosphorus solvents for rare earth element recovery.
 Nuclear fuel reprocessing:
 PUREX process: Plutonium and uranium recovery from spent
nuclear fuel.

5. Food and Beverage Industry

 Decaffeination of coffee and tea:
o Using solvents like methylene chloride or ethyl acetate to remove caffeine.

 Extraction of flavors and colors:

o From natural products such as herbs, spices, and fruits
 Purification of organic acids:
o E.g., citric acid or lactic acid extraction from fermentation broth.

6. Environmental Applications
 Wastewater treatment:
o Removal of phenols, oils, pesticides, and organic contaminants.

 Treatment of industrial effluents:

o Recovering solvents, acids, or other reusable chemicals before
discharge.

 Oil spill cleanup:

o Extraction of spilled hydrocarbons from water bodies using specific
solvents.

7. Biotechnology and Biochemical Applications

 Downstream processing of bioproducts:

o Extraction of enzymes, vitamins, proteins, or antibiotics from
fermentation systems.

In-situ product recovery:

o Continuous extraction of inhibitory by-products to enhance yield.

8. Laboratory-Scale Applications
 Analytical chemistry:
o Sample preparation, purification, and concentration .
  Organic synthesis:
o Work-up steps to isolate desired products from reaction mixtures.

Summary of Key
Applications

Industry Main Application

Chemical Separation and purification of
chemicals
Pharmaceutical API purification, antibiotic recovery
Petrochemical BTX recovery, desulfurization, lubricant refining
Metallurgical Metal extraction (U, Cu, Co, REEs)
Food & Beverage Decaffeination, flavor extraction
Environmental Wastewater treatment, solvent recovery
Biotech/Biochemical Extraction of bioproducts, enzymes, vitamins

Conclusion:
Liquid-liquid extraction is a powerful and versatile separation technique widely
used across various industries for recovering, purifying, or separating valuable
components from complex mixtures. The effectiveness of this process relies
heavily on the selection and proper operation of extraction equipment, such as
mixer-settlers, centrifugal extractors, packed columns, and rotating disc contactors.

Each type of equipment has specific working principles, advantages, and

limitations, making it suitable for particular process requirements, whether in batch
or continuous mode. By understanding the working limits, such as flow rates,
density differences, interfacial tension, and viscosity, operators can optimize
performance and avoid operational challenges like flooding, emulsification, or
inefficient separation.

The wide range of applications—from metal recovery, pharmaceutical

purification, and fuel processing to food and environmental cleanup—highlights
the industrial importance of liquid-liquid extraction. With continuous
advancements in design and automation, extraction equipment is becoming more
efficient, compact, and environmentally friendly.

In summary, liquid-liquid extraction, when properly designed and operated, offers

a highly selective, efficient, and economical method for complex separations,
making it an essential unit operation in modern chemical engineering and process
industries.