SURFACTANT BASED SEPARATIONS

UNIT-III
 Contents
• Introduction to surfactant based separations

• Surfactants and examples

• Working pattern

• Classification / Types of surfactants

• Critical micellar concentration

• Illustration: Surface tension driven interfacial mixing

• Mechanism

• Adsorptive Bubble Separations

• Bubble and Foam Fractionation

Surface Tension examples in Daily life
• Surface Tension: "The property of the surface of a liquid that allows it
to resist an external force, due to the cohesive nature of its
molecules.“

• Surface tension is the tendency of liquid surfaces at rest to shrink into

the minimum surface area possible.

• Surface tension is what allows objects with a higher density than

water such as clips, razor blades, insects to float on a water surface
without becoming even partly submerged.

• Unit: Newton per metre in SI or dynes per centimeter in CGS

system.

• Surface Tension γ = F / 2L
 Introduction
• An emerging technology.

• Employed in practical situations, viz.

removal of detergents from laundry wastes, (the Indian laundry services
market has grown significantly in recent years and is estimated to be worth over Rs
20,000 crores. The industry is expected to continue its growth trajectory at a CAGR of
7.5% over the next five years)

ore flotation, mineral processing industries,

removal of oil from waste waters etc.

Separations:
With/by the use of surfactants or removal of surfactants
 Ore Flotation
• In mineral processing, method used to separate and concentrate ores
by altering their surfaces to a hydrophobic or hydrophilic condition;
that is, the surfaces are either repelled or attracted by water.
 What are surfactants?
• Also called surface active compounds.
• Substances when added into liquids in small amounts, appreciably
lower the surface tension of those liquids.

E.g. Detergents, Alkyl benzene sulfonate (ABS), Linear alkyl benzene

sulfonates (LABS), Lignin sulfonates, fatty alcohol ethoxylates, alkyl
phenyl ethoxylates etc.

 Addition of surfactants in small amounts in liquids increases

spreadability, wettability and similar properties that are dependent
on surface tension.
 Contd….
• Surfactants lower the surface tension (interfacial tension) between
two liquids, between a gas and a liquid or between a liquid and a
solid.

• Surfactants act as detergents, wetting agents, emulsifiers, foaming

agents and dispersants.

Dispersants (a liquid or gas used to disperse small particles in a medium)

Soap powder.
Turkey red oil.
Alkyl sulphonates.
Alkyl acryl sulphonates.
Formaldehyde.
Lignin sulphonates.
 Emulsification
Emulsification is the process
by which the dispersed
phase is broken up into small
droplets.

Inorganic emulsifying agents: Milk of

magnesia.
Cationic emulsifying agents:
Benzalkonium Chloride.
Anionic emulsifying agents: Sodium
lauryl sulfate (SLS)
Non-ionic emulsifying agents: Glyceryl
ester.
 Wetting
Wetting agents or detergents (e.g., sodium lauryl sulfate, quaternary
ammonium compounds, and non-ionic surfactants, such as Triton X-100)
lower surface tension to enable liquid penetration
How surfactants work?
Aqueous surfactants, typically are amphiphilic molecules.
Have one portion of molecule which is polar (water loving) and
another non polar (water fearing).

Water loving: Hydrophilic, are heads

Water fearing: Hydrophobic, are tails
• Example: HEXADECANOL; Molecular formula: CH3(CH2)14 CH2OH
• Polar part is OH group, rest is non polar.
• Polar part (OH) is more compatible with water, while non polar part is
less compatible.

• Surfactants when added into water (72 dynes/cm @ 25 ̊C), the

surface tension greatly reduces, thereby
spreadability of water
wettability of water and
elasticity of water significantly increases.

• Due to increase in elasticity, water film remains intact and continuous

without breaking.
Breaking of water-film is due to local disruptions within, which can be avoided by
using a surfactant.
 Working pattern
Water (high ST; 72 dynes/cm @25 ̊C)

Local disruptions more, causing water film to break

(due to inherent high ST and low elasticity)

Add surfactant

ST decreases appreciably

Water film remains continuous without breaking

(due to increase in elasticity)

Outcome: Water (without surfactant) Water (with surfactant)

Elasticity; low (discontinuity) Elasticity; high (continuity)
 Classification of surfactants
• Classified based on polar head group.
i. Non ionic surfactant; no charged groups in its head. E.g. Ethoxylates

TAIL, water fearing HEAD, water loving

ii. Anionic surfactant, negative charged groups in its head. E.g. Sulfate, sulfonate, phosphate
esters, sodium dodecylsulfate (SDS) etc.

iii. Cationic surfactant, positive charged groups in its head. E.g. Quaternary ammonium salts,
cetyl pyridinium chloride (CPC) etc.
+

iv. Amphoteric surfactant (zwitterionic or zwitternic), both positive and negative charges in its
head. E.g. Phospholipids, sphingomyelins etc.
+-
 Critical micellar concentration
• Any surfactant molecule has hydrophilic head and hydrophobic tail.
• At lower surfactant concentrations, they are aligned across the
water-air interface, where the hydrophobic tail point towards the air.

AIR

WATER

• When the concentration of surfactant increases further, the

surfactant molecules come to the bulk to attain the minimum volume
to surface ratio (which is thermodynamically more stable) and they
form spherical globules called micelles.
 Contd..
• In micelles, the surfactant molecules are aligned such that hydrophilic
heads point towards the aqueous solution phase and the
hydrophobic tails form the core.

Head
Core
Aqueous phase

Tail

• Therefore micelles have polar hydrophilic characters on its surface

and the core is hydrophobic.
• The concentration of surfactant at which this happens is called
critical micellar concentration (CMC).
Stages of micelle formation
 Illustration: Surface tension driven interfacial mixing
Case: Absorption-desorption
E.g. Absorption of water vapour from air into liquid ethylene glycol (EG).
“UNSTABLE SYSTEM”
EG: (C2H6O2), serves as a dewatering agent, also antifreeze, a coolant, hydraulic brake fluids,
ballpoint pens, solvents, paints, plastics, films, pharmaceuticals and cosmetics.

GAS
Humid air (air + water vapour)
water

LIQUID
Water-rich
Liquid ethylene glycol Glycol-lean
(High ST)
Circulation currents
Glycol-rich
Water-lean
(Low ST)
 Contd…
• Desorption of water from ethylene glycol into air. “STABLE SYSTEM”

water

GAS
Air

Water-lean
LIQUID Glycol-rich
EG + water (Low ST)
No Circulation currents
Water-rich
Glycol-lean
(High ST)
 Mechanism
• Surface tension of pure water 72 dynes/cm @25 ̊C.

• Surface tension of EG 48 dynes/cm @25 ̊C. (ST of water ˃ ST of EG)

• During absorption, water vapour from air gets absorbed into EG.

• A water-rich layer develops near the interface compared with bulk

liquid, liquid near the interface has a higher surface tension than the
bulk liquid.

• Therefore circulation currents or patterns develop. (Marangoni effect)

• Due to circulation patterns, the liquid phase mass transfer

coefficient, KL increases or 1/KL decreases.

• Situation is Unstable.
 Contd…
• In desorption, liquid near the interface has low inherent ST (glycol-
rich) than the bulk liquid.

• No circulation currents develop.

• Situation is Stable.
 Marangoni effect
• The Marangoni effect is the mass transfer along an interface between
two phases due to a gradient of surface tension.

• Since a liquid with a high surface tension pulls more strongly on the
surrounding liquid than one with a low surface tension, the presence
of a gradient in surface tension will naturally cause the liquid to flow
away from regions of low surface tension.

• The surface tension gradient can be caused by concentration gradient

or by a temperature gradient.

• Surface tension is a function of temperature.

 Tears of Wine
• Wine may exhibit a visible effect called "tears of wine".
• The effect is a consequence of the fact that alcohol has a lower surface tension and
higher volatility than water.
• The water/alcohol solution rises up the surface of the glass lowering the surface
energy of the glass.

• Alcohol evaporates from the film leaving behind liquid with a higher surface
tension (more water, less alcohol). This region with a lower concentration of
alcohol (greater surface tension) pulls on the surrounding fluid more strongly than
the regions with a higher alcohol concentration (lower in the glass).

• The result is the liquid is pulled up until its own weight exceeds the force of the
effect, and the liquid drips back down the vessel's walls.

• This can also be easily demonstrated by spreading a thin film of water on a smooth
surface and then allowing a drop of alcohol to fall on the center of the film. The
liquid will rush out of the region where the drop of alcohol fell.
 Adsorptive Bubble Separations

Foam separations Non foaming separations

Froth flotation Foam fractionation

Bubble fractionation Solvent sublation or
ion flotation

Combined Bubble / Foam fractionation

Ore flotation
Macro flotation
Micro flotation
Precipitate flotation
Colloidal flotation Solvent sublation: Type of Adsorptive Bubble separation.
Molecular flotation Surface active compounds (hydrophobic) in aqueous phase
are adsorbed on the bubble surfaces of an ascending gas
stream and then collected in an organic layer placed on top
of the aqueous phase.
 Bubble and Foam Fractionation
Characterization:
• Name: BFF (Bubble and Foam Fractionation)

• Feed: Liquid

• Separation agent: Rising air bubbles and complexing surfactants.

• Products: Two Liquids

• Principle of separation:
Tendency of surfactants to accumulate at the G-L interface and rise
with air bubbles.

• Practical example:
Detergents removal from laundry wastes, ore flotation etc.
 Schematic (BFF)

Foam Foam
(A) (B)

Liquid feed

Liquid feed
having
surfactant
neodol
Surfactant
within and
(separately added)
to be
removed
more conc. in
also has
the column
certain
cations
Cu2+ Air
Air
Liquid raffinate Liquid raffinate
 Neodol

• Shell NEODOL alcohols and alcohol ethoxylates are found at the heart
of many everyday products.
• They help to keep our clothes, floors and dishes clean.
• The NEODOL 91 series alcohol ethoxylates are widely used for their
extreme versatility.
• NEODOL 91-6 is particularly suited for surface cleaning, laundry
detergents and vehicle cleaning.
• Typical properties of this alcohol ethoxylates include cleansing,
foaming, detergency, wetting and emulsification.
 Process description
In figure (A);
• Feed liquid flows downwards.

• Gas (air) rises up (fine bubbles).

• Foaming occurs above the feed level.

• Later withdrawn as an overhead.

• During which the surfactants get adsorbed to the bubble surfaces and
leave in the foam product.
 Axial concentration profile for NEODOL (anionic surfactant)
(figure A)
• Specifications:
Column diameter = 6.95 cm
L/D ratio ˃ 20
Volume gas-liquid ratio = 1.88
Neodol concentration in the feed = 19.6 ppm
Feed level = 150 cm above the bottom
20
Neodol being an anionic surfactant,
it has a property of pairing
selectively with certain cations, viz.
Neodol Cu2+.
conc. Surfactant entering along with
ppm copper bearing feed solution, the
counter flowing gas and liquid in the
bubble column would accomplish
relatively little fractionation of Cu,
since not much surfactant is
available in the column.
0 150
Height in cm above the bottom
 Axial concentration profile; separate surfactant added
(figure B)
• Specifications:
Column diameter= 6.95 cm
Cu concentration in the feed = 0.078 m mol/m3
Surfactant feed level = 30 cm above the bottom
Main feed level = 150 cm above the bottom
0.08 It is stated that the fractionation
reduces the Cu concentration by
a factor of 3 in the bubble
section
Liquid
phase
conc.
mmol/m3

0 150
Height, cm above the bottom
 Final remarks
• Combined bubble and foam fractionation are promising processes
for treatment of effluent waters, down to ppb.

• Surfactants cause elasticity and have film stabilizing properties.

• Many surfactants serve to generate and promote foams.

Employed in practical situations, viz. removal of detergents from

laundry wastes, ore flotation, mineral processing industries,
removal of oil from waste waters etc.
 Recent Update
American Oil Association of Engineers and Chemists
Enhanced Oil recovery by Green surfactants
• Generally, surfactants affect the processes of oil recovery through
four main mechanisms: interfacial tension reduction, wettability
alteration, foam generation and emulsification.

• Anionic surfactants are most widely used in chemical EOR because of

their negative charge.
Green Surfactants
 Applications of green surfactants
Surfactants in food industry:
• Due to their unique chemical structure, surfactants strongly affect the stability of
colloid systems and can interact with all the main components of flour (starch,
gluten and lipids).
• Surfactants are often used in the creation of food emulsions. These act as binding
agents, allowing unlike molecules to adhere to each other.
Mayonnaise is a common kitchen emulsion which uses a surfactant.

Surfactants in agriculture industry:

• Different surfactants can be used as wetting agents, dispersants, or emulsifiers. In
the case of wetting agents, their main use is as co-adjuvants in the application of
various crop treatments, while dispersants and emulsifiers are usually added to
provide stability to agricultural input formulations.

• Adjuvant: A substance that enhances the body's immune response to an antigen.

Adjuvants have been used safely in vaccines for decades.
Aluminum salts, such as aluminum hydroxide, aluminum phosphate, and aluminum
potassium sulfate have been used safely in vaccines for more than 70 years.
Surfactants in pharmaceutical industry:
• The nonionic surfactants products mainly serve as emulsifier, wetter, solubilizer and
dispersant in pharmaceutical industry. As gelling agent and foaming agent, they are
used in the manufacture of several forms of drugs such as emulsion, cream,
suppository, tablet and capsule etc.

Surfactants in drug delivery:

• Surfactants are amphiphilic molecules of great interest in the pharmaceutical field
which are used in combination with other adjuvants to solubilize poorly soluble
drugs, improve their dissolution profile, promote permeation, improve drug
delivery and enhance stabilization.
 Miscellaneous surfactants

• Sorbitan Esters (Spans)

• Sucrose Esters

• Glucose-Derived Surfactants

• Alkyl Poly glycoside (APG) Derivatives

• Carboxylic acid/quaternary ammonium

(e.g., lauryl-N,N-dimethyl ammonium butyrate)

• Sulfuric acid/quaternary ammonium (e.g., surfactin)

• Phosphoric acid / quaternary ammomium phospholipids.

• Miscellaneous (e.g., lauryl dimethylamine N-oxide)

LIQUID MEMBRANES, LMs

UNIT-III
 Contents

• Introduction

• LMs

• Constitution of LMs

• Features of LM separations over other MSPs

• Types of liquid membranes (LMs)

• Transport in a Liquid Membrane

• Advantages and disadvantages of LMs

• Applications of LMs
 Introduction
• Membranes containing an immiscible solvent and a carrier.

• Immiscible solvent liquid will act as a membrane/separation barrier

between two phases.

• A carrier facilitates selective transport of gases or ions.

• A carrier is organic and also reactive within the membrane.

• It reacts with and helps transport one of the components of the feed
across the membrane.
 LMs
• These are held within the micro pores of membrane by the capillary
action.
• Also called “carrier facilitated transport”.
• Since a carrier used is specific, a high membrane selectivity can be
achieved.

Status:
• No. of commercial plants are available in countries like China, Austria.

• Due to high initial cost and maintenance cost, this is yet to be

commercialized in India.
 Constitution of LMs
• Three main components:
1. Micro porous polymeric thin
film; porous support membrane

2. Organic carrier phase

(reactive)
FACILITATES TRANSPORT OF
IONS/SPECIES

3. Immiscible organic liquid

solvent filled pores (inert)
MEMBRANE/BARRIER
• Porous support membrane
Frame work to hold the liquid solvent within its pores. (as a free liquid
film is not very stable)

Surface porosity and overall porosity of supports should be high.

(to obtain optimal flux)

Membrane should be as thin as possible. (flux is inversely

proportional to the membrane thickness)

Materials used are PP, PTFE, PE etc.

*** Stretching and phase inversion are the techniques of preparation

• Organic carrier phase (reactive)
Organic in nature.

Specific to one solute. (to obtain high selectivity)

Dissolved carrier agent will be held by the capillary action in the

pores of a micro porous film.

Carrier concentration (CC): Two counteracting effects are seen.

i. If CC increases, entering flux increases.
ii. If CC increases, viscosity also increases; while diffusivity decreases.

Class of carrier molecules used are:

Tertiary Oximes (LIX 64 N, Kelex 100), amines, crown ethers (cyclic
chemical compounds that consist of a ring having several ether
groups), cobalt complexes, PEG, naphthenic acids etc.
 LIX 64N Reagent is a water insoluble mixture of substituted oximes, which form water insoluble
complexes with metallic cations, principally copper.
• Organic liquid solvent (inert)
Must be solvent for both carrier and carrier-solute complex.
Low viscosity.
Solvents used in LMs are:
Solvents Viscosity (g/cm-sec )@25 ̊C
O-dichlorobenzene 0.013
1- Octanol 0.076
O- nitrophenyl octyl ether 0.128
Dibutylphthalate 0.154
O-nitrodiphenyl ether 0.161
 Features of LM separations over other MSPs
LMs have some attractive features….

• Simple operation, high efficiency, extraction and stripping in one

stage, larger interfacial area and scope of continuous operations.

• The problems like low mass transfer rates, low selectivity, large size
requirements etc. generally seen in usual MSPs like MF, RO, Dialysis,
UF etc. are all overcome by LMs.

• For all these reasons,

LMs is taken to be promising and potentially
powerful technology for effecting a diverse no. of separations.
 Types of liquid membranes (LMs)

• Supported Liquid Membrane (SLM) or

Immobilized Liquid Membrane (ILM)

• Emulsion Liquid Membrane (ELM) or

Bubble Liquid Membrane (BLM)
 Supported Liquid Membrane
High conc. Low conc. Also called Immobilized Liquid Membrane.
Micro
porous Made by immersing a thin porous film of
polymeric suitable solid substance with a liquid.
thin film
Liquid is immiscible solvent, organic in
nature.

Pores in the film are occupied by this

liquid.

Organic carrier Membrane thickness is generally about 20-

phase 150 μm.
(reactive)
Molecules diffuse through the liquid in the
pores.

Immiscible To facilitate the transport, an organic

organic liquid reactive carrier is used.
solvent filled
pores (inert) This carrier is specific and selective to
react with a particular solute in the feed.
 Emulsion Liquid Membrane
Organic membrane Organic
containing a carrier carrier phase
Aqueous product solution

Also called Bubble Liquid Membrane.

Involves the use of a surfactant

stabilized emulsion.

The organic phase forms the wall of

an emulsion droplet separating the
aqueous feed from the aqueous
product solution.
Aqueous feed
solution
These bubbles or droplets or
globules have the size in the range of
0.5 to 10 μm
 Liquid Membrane modules
• Immobilized Liquid Membrane or Supported Liquid Membrane
module:
Stirrer
The ILM is set between source and receiving
SLM/ILM
phase.

System of gentle stirring is employed.

Speed of stirring is 100 to 300 rpm.

Stirring is adopted to create stability in a

system.

Instability may be due to the use of a carrier

agent or organic inert liquid in pores.
Source Receiving
phase phase Overall mechanism is based on solution
diffusion model.

Stability in a system is also attained by

i. Solvent liquid or carrier evaporation
ii. Creating a large pressure difference across
the LM, effectively pushing out the fluid.
• Emulsion Liquid Membrane module:

Stirrer Metal ions are concentrated in the interior of

the droplets.

Source phase When sufficient metal has been extracted,

the emulsion droplets are separated from the
feed.
Receiving
phase
Then broken to liberate the concentrated
product solution and an organic carrier
phase.

The carrier phase is decanted from the

product solution and recycled to make more
emulsion droplets.

Breaking of emulsion droplets:

Sedimentation, flocculation, centrifugation,
Ostwald’s ripening, Ultrasonic bath etc.
 Transport in a Liquid Membrane
Three types of transport.
• Passive diffusion
• Facilitated transport
• Coupled transport Passive diffusion down a
concentration gradient is the
Passive Diffusion most familiar and common.

Process is relatively slow and

non-selective
High Low
activity activity
phase phase
• Passive diffusion/transport:

One example of passive transport is diffusion, when molecules move

from an area of high concentration (large amount) to an area of low
concentration (low amount).
Molecules are said to naturally flow down their concentration
gradient.
This type of diffusion proceeds without an input of energy.
 The liquid membrane phase
contacts a carrier agent that
Facilitated transport chemically combines with the
Carrier: Hemoglobin permeate to be transported.

Upstream side, hemoglobin

HEM reacts with oxygen to form
membrane oxy-hemoglobin, which then
Oxygen diffuses to downstream side.
Oxygen
[HEM-O2] Here on the downstream side,
the reaction is reversed.

Oxygen is liberated to the

permeate gas and hemoglobin
O2 + HEM [HEM-O2] [HEM-O2] HEM + O2 is reformed.

Hemoglobin diffuses back to

the feed side of the
membrane to take up more
oxygen, while other gases like
nitrogen that do not react
with hemoglobin are left
behind.
Coupled Transport (Permeation of copper and hydrogen ions across a membrane
using a reactive oxime as a carrier)
HR

Cu2+ Cu2+

Membrane
H+
CuR2 H+

Cu2+ + 2HR CuR2 + 2H+ CuR2 + 2H+ 2HR + Cu2+

Coupled transport is analogous to performing solvent extraction in a

thin liquid film.
The majority of liquid membranes for metal ion separation involve a
coupled transport mechanism.
 Schematic Diagram of the Coupled Transport Mechanism for Metal Ion Transport
Through a Liquid Membrane.
M + is the metal ion, HC is the ion-exchange reagent (carrier), and
H + is a hydrogen ion.
 Oxime: A chemical compound belonging to imines.
General formula: RŔC = NOH

Oximes used as metal extractant, ligands, sequestration agents,

chelating agents, antidotes for nerve agents, oil based paints etc.

Sequestration agent: A chemical whose molecular structure can envelop and hold
a certain type of ion in a stable and soluble complex.

Chelating agents: are chemical compounds that react with metal ions to form a
stable, water-soluble complex. They are also known as chelants.

Nerve agents or nerve gases: Weapons of chemical warfare that affects the
transmission of nerve impulses through the nervous system. The organo phosphorus
nerve agents Tabun, Sarin, and Soman were developed by Germany during World War
II but not used. Later also developed VX also called venomous agent X.
• Couple transport resembles facilitated transport. In facilitated
transport, a carrier agent is incorporated in the membrane while in a
coupled transport, the carrier agent couples the flow of two species.

• Due to this coupling, one of the species can be moved against its
concentration gradient, provided the concentration gradient of the
second couple species is sufficiently large.

• In the figure, the carrier is an oxime that forms an organic soluble

complex with copper ions.

• The reaction is reversed by hydrogen ions.

• On the feed side of the membrane two oxime carrier molecules pick
up a copper ion, liberating two hydrogen ions to the feed solution.
The copper-oxime complex then diffuses to the downstream membrane
interface, where the reaction is reversed because of the higher
concentration of hydrogen ions in the permeate solution.

The copper ion is liberated to the permeate solution and two hydrogen
ions are picked up.

The reformed oxime molecules diffuse back to the feed side of the
membrane. It is often called liquid membrane transport.
 Advantages and disadvantages of LMs
Advantages:
• Cleaner separation due to carrier facilitated transport.
• Higher selectivity to different phases due to chemical nature.
• Extraction and stripping taking place simultaneously in one stage.
• Membrane fluid corresponds to solvent of usual solvent extraction
rather, smaller solvent requirements.
• Uphill transport characteristics, low solvent loss, high interfacial area
per unit volume, low possibility of concentration polarization.

• Disadvantages: (Major)
• Stability of LMs is a drawback.
• High initial capital investment and maintenance costs.
 Uphill Transport

Uphill transport involves movement of molecules from a region of lower

concentration to higher concentration against the concentration
gradient with the expenditure of energy.

 Active is Uphill; Passive is Downhill

 Applications of LMs
• Recovery of copper, cadmium, nickel and lead ions from dilute
aqueous solutions and waste waters.
• Extraction of ground water contaminants viz. arsenic, uranium etc.

• CO2 / H2S separations.

• Olefin separations.

• O2 /N2 separations.

• Phenol removal from waste waters.

• Biochemical and biomedical applications.