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20 views45 pages

Branch: Chemical Sem: 6 Prepared By: Sri YK Mohanta: Lecture Notes of Nobel Separation Technology

Uploaded by

Awas Deshmukh
Copyright
© © All Rights Reserved
We take content rights seriously. If you suspect this is your content, claim it here.
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You are on page 1/ 45

LECTURE NOTES OF

NOBEL SEPARATION TECHNOLOGY


Branch: Chemical
Sem: 6th
Prepared by : Sri YK Mohanta
( Lecturer in Chemical,UCPES Berhampur)

CHAPTER 1 : INTRODUCTION

Separation is an indispensable part of


downstream operation in chemical,
petrochemical, biochemical, food and several
other allied process industries. It is needed to
achieve the goals of enrichment, concentration,
purification, refining and isolation of any
desired product from a mixture. Efficient
separation processes are also required to
obtain high-value products in the food and
pharmaceutical industries, to supply
communities and industry with high quality
water, and to remove and recover toxic or
valuable components from industrial effluents.
Equilibrium and rate governed separation:
In general, separation processes of fluid
mixtures can be divided into two categories:
equilibrium separation and rate governed
separation. Conventional separation processes
such as evaporation, distillation, extraction,
adsorption and absorption.

if separation is based on differences in


transport rate through some medium under the
influence of a driving force resulting from a
gradient in pressure, concentration,
temperature, or electrical field, it is termed as
rate governed separation.

Membrane:
The membrane can be defined essentially as a
barrier which separates two phases and
restricts transport of various chemicals in a
selective manner.

The membrane can be a selective or a


contacting barrier. In the former case, it
controls the exchange between the two regions
adjacent to it in a very specific manner, whereas
in the latter case, its function is mainly to
contact the two regions between which the
transport occurs. Contrary to the conventional
mass transfer operations, the two phases
between which transfer of one or more species
occurs are not in direct contact in membrane
separation.

A membrane can be homogenous or


heterogeneous, symmetric or asymmetric in
structure, solid or liquid, can carry a positive or
negative charge, or can be neutral or bipolar.

Transport through a membrane can be effected


by convection or by diffusion of individual
molecules induced by an electric field or
concentration, pressure or temperature
gradient. Membranes can also physically or
chemically modify the permeating species (as
with ion exchange or biofunctional
membranes), prevent permeation (e.g. in
packaging or coating applications) or regulate
the rate of permeation (as in controlled drug
delivery). Thus membranes may be either
passive or active, depending upon the
membrane's ability to alter the chemical nature
of the permeating species. The membrane
thickness may vary from as small as 100 micron
to several millimetres. Another characteristic
property of membrane is its permselectivity,
which is determined by differences in the
transport rates of various components in the
membrane matrix.

Basic principe of membrane separation:


Porous membranes discriminate according to
the size of particles or molecules. Non porous
membranes discriminate according to the
chemical affinities between components and
membrane materials.

The thinner the membrane, the higher will be


the flux.
From the thermodynamic point of view, there
may be three types of transport through
membrane. These are active transport, passive
transport and facilitated or carrier mediated
transport.
In a system characterised by a single force and
a single flow, the flow must be directed from a
region of higher electrochemical potential to
one of lower electrochemical potential.
The term 'active transport' should be applied to
flows that are directed against their conjugate
driving forces and conversely the passive
transport' are those where flows are directed in
the direction of conjugate driving force.
In facilitated or carrier mediated transport, the
carrier molecules which reside in the
membrane, can interact with a given permeant.

Classification of membrane processes:


Membranes for industrial separation can be
broadly classified into the following four
groups according to the driving force that
causes the flow of the permeant through the
membranes:
1. Pressure driven membrane process:
• Reverse osmosis (RO)
• Nanofiltration (NF)
• Ultrafiltration (UF)
• Microfiltration (MF)
• Pervaporation (PV)
• Membrane gas separation
2. Concentration gradient driven membrane
process:
• Dialysis
• Membrane extraction

3. Electrical potential driven membrane


process:
• Electrodialysis (ED)

Advantages of membrane processes:


Membrane processes provide a highly flexible
separation technique for selective solute
separation/concentration, and permeate
recycling and reuse. The special features for
membrane processes that make them attractive
for industrial applications are their
compactness, ease of fabrication, operation and
modular design.
Appreciable energy savings: An advantage of
membrane technology as compared to
conventional processes is that it permits
concentration and separation without the use
of heat. Since membrane separations do not
require a change in the state of the solvent
(except for pervaporation) to effect a
dewatering, this should result in considerable
savings in energy.

Clean technology with operational ease: No


complicated heat transfer or heat generating
equipment is needed in membrane operations.
These processes can be operated at ambient
temperatures. A further advantage over
evaporators is that no condenser is needed;
thus avoiding related problems like thermal
pollution and sewage water.

Replaces the conventional processes: Existing


non-membrane based equilibrium driven
separation technologies (e.g. adsorption,
absorption, extraction, distillation and
stripping) may have significant shortcomings:
inherent operational difficulties
(emulsification, foaming, entrainment,
weeping, etc.), lack of flexibility (flooding,
loading and need for density difference), slower
rate, lack of modularity, and the need for large
space. These shortcomings are mitigated by
membrane processes.

Recovery of high value products: As technology


develops, more and more situations arise
where substance of high unit value are formed
in very low concentration. In conventional
separation processes, the separation efficiency
drops rapidly as the concentration of the
desired component falls. Membrane separation
techniques, on the contrary, can give better
answer to these problems.

Greater flexibility in designing systems: With


the development of new membranes with
improved transport properties and better
chemical and thermal stability in recent years,
a large number of new potential applications
are identified.
Hybrid process development: It is more
advantageous to use both distillation and
membrane unit operations in series. The hybrid
can successfully increase capacity of existing
plants and improve product quality. A hybrid
process is successful if its overall cost and
performance is an improvement over the
individual alternatives.

Disadvantages of membrane separation


processes:

Membrane separation processes do suffer from


certain disadvantages which lead to its
application constraints. Some of the
disadvantages are stated below:
Membrane fouling: Membrane fouling is a
pertinent problem in membrane separation
process. Contaminated feed increases the rate
of membrane fouling, especially for hollow
fibre modules.

Upper solid limits: In fact, membrane processes


are quite limited in their upper solid limit. In
RO, it is frequently the osmotic pressure of the
concentrated solutes that limits the process. In
the case of UF and MF, it is rarely the osmotic
pressure of the retained macromolecules, but
rather the low mass transfer rates and high
viscosity that makes the pumping of the
retentate difficult.

Expensive: In general membrane processes are


expensive compared to other processes. It is
due to the fabrication method, occasional
replacement, fouling & poor cleanability of the
membrane.

Major areas of application:


Membrane processes are no longer bound in
the domains of laboratory but processes have
achieved impressive industrial in many
applications.

Chemical Industry:
Membrane separation has emerged as the most
important and practically useful 'modern
separation technique' in chemical process
industries. Some of the major applications are:
• Production of process water for industrial
use.
• Waste water treatment.
• Desalting of food, acid and reactive dyes.
• Concentration of all types of dyes

Pharmaceutical Industry:
In pharmaceutical and cosmetic manufacturing,
membrane technology assumes importance in
the success of many new products and
processes, while traditional processes have
been changed over to membranes with
dramatic cost savings and improved yields. Due
to the macromolecular nature of most
bioengineered products, Membrane processes
are already playing a key role in the following
processes:
• Concentration and purification of soluble
macromolecules such as plasma proteins,
vaccines, enzymes and yeasts
• Process water as per USP standards
• Endotoxin free water

Food and Dairy Industry:


Though the applications have been few, yet the
potential is very large and will provide energy
saving, processing without phase change and
higher recovery of quality products. Following
are the various membrane processes used in
milk processing industries:
• Lactose and protein concentration
• Concentration of whole and skim milk
• Lactose protein separation
• Fractionation and concentration of egg
albumin and animal and fish oils and proteins
• Concentration of extracts of vanilla, lemon
peel, malt, etc.

Biotechnology Industry:
Some major areas of membrane application in
biotechnology are as follows:
• Enzyme concentration
• Fermentation broth clarification
• Separation of microsolutes like antibiotics
and vitamins
• Purification and concentration of vitamins
• Tissue culture reactor systems

Future prospects:
• Developing new membrane materials.
• Identification of new ways of using
permselective membranes.
• Combining conventional unit operations and
membrane separation processes, which often
results in separation processes that offer
significant advantages over individual
processes.

CHAPTER 2: MEMBRANE TYPE,


MODULE & FLOW PATTERN
The choice for a certain kind of membrane
depends on number of factors as:
• Good permeability.
• Chemical stability and compatibility.
• Mechanical strength.
• Resistance to fouling.
• Ability to cast into a thin film.
• Pore characteristics.

Classification of membranes:
On the basis of nature of the membrane:
• Natural
• Synthetic

On the basis of structure of the membrane:


• Porous
• Nonporous

On the basis of Pore geometry:


• Cylindrical
• Spongelike
• Modular

On the basis of Final morphology:


• Woven
• Sintered
• Cast and extruded
• Irradiated

Microporous membranes:
- A microporous membrane is very similar in

structure and function to a conventional filter.


It has a rigid, highly voided structure with
randomly distributed, and interconnected
pores.
- However, these pores differ from those in a

conventional filter by being extremely small,


on the order of 0.01 to 10 μm in diameter.
-All particles larger than the largest pores are
completely rejected by virtue of a sieving
effect.
The microporous membranes are further
classified as:
• Isotropic: Here the pores are of uniform size
throughout the membrane; and
• Anisotropic: Here the pores change in size
from one surface of the membrane to the
other.

Microporous membranes are designed to retain


all particles above its rating. For example, a
0.45 µm membrane implies that it will not allow
particles larger than 0.45 um to pass through it.
However, this does not mean that the size of the
pores is 0.45 µm or less.

Asymmetric membrane:
- Also known as skinned membrane.
- These are characterised by a thin(0.1 to 1

micron) skin on the surface of membrane.


- There is one porous sub-layer underneath

which acts as a support for the thin, fragile


skin and has little effect on the separation
characteristics.
- It’s separation characteristics are determined
by the nature of membrane or pore size and
mass transfer rate is determined mainly by
the skin thickness.

Asymmetric membranes are again of two types:


• Integrally skinned: skin layer resulting from
phase inversion process which are porous.
• Non-intergrally skinned: skin layer that are
deposited from the solution and are
homogeneous in nature.

Thin film composite membrane(thin layer


composite):
- Also known as second generation membrane.
- These membranes are primarily designed for

RO and NF applications.
- Thin film composite have a thin dense

polymer skin formed over a microporous


support.
- These are available in spiral, plate & frame and

tubular module configurations.


- These membrane requires a very finely
porous substrate to which the film can adhere
well.
- For adequate film support, the pores in the
substrate must be smaller in diameter than
the thickness of the film to be applied.

Electrically charged membrane:


- These are necessarily ion exchange
membrane membranes consisting of highly
swollen gel carrying fixed positive or negative
charge.
- Electrically charged membranes can be

dense or microporous , but are most


commonly very finely microporous with the
pore walls carrying fixed positively or
negatively charged ions.
- A membrane with fixed positively charged

ion is referred as anion exchange membrane


because it binds anions in the surrounding
fluid. Similarly a membrane containing fixed
negatively charged ions is called cation
exchange membrane.
- Here separation is achieved mainly by the
exclusion of ions of ions of the same charge
and to a much lesser extent by the pore size.
- These are mainly used in electrodialysis.

Inorganic membrane(Ceramic membrane):


- They are versatile and can be operated at

elevated temperature.
- Metal membranes are stable at temperatures

ranging from 500-800°C and many ceramic


membranes are usable at over 1000°C.
- They are also much more resistant to chemical

attack.
- Because of the wide variety of materials that

may be used in the fabrication of the inorganic


membranes, they are also resistant to
corrosive liquid and gases.
- Ceramic membranes normally have an
asymmetrical structure composed of at least
two, but mostly three, different porosity
levels.
Membrane module:
The device in which the membranes are
installed is known as membrane module.
(or)
Membrane module is the smallest unit into
which the membrane are is packed.

The membranes can be cast as flat sheets, tubes


and fine hollow fibres. For accommodating such
shapes and structures, different types of
membrane modules are available. There are
basically four different designs of membrane
modules which are most commonly used. These
are:
(a) Plate and frame
(b) Tubular
(c) Spiral wound
(d) Hollow fibre

The choice of module configuration as well as


the arrangement of modules in a system
depends on:
- Economic considerations.
- Type of separation problem.
- Ease of cleaning.
- Ease of maintenance and operation.
- Ease of compactness of the system.
- Scale and possibility of membrane
replacement.

Plate and frame:


- This is also known as flat sheet Tangential

Flow(TF) module.
- These are similar to plate and frame filter

press with a series of flat membrane sheets.


- Here sets of two membranes are placed in a
sandwich like manner with their feed sides
facing each other.
- In each feed and permeate compartment, a
suitable spacer(support screen) is placed.
- The units may have square, rectangular or
oval cross-section.
- Sometimes to reduce channelling(i.e. the
tendency to flow along a fixed pathway) and
to establish uniform flow distribution, so
called ‘stop discs’(baffles) can be introduced.

Advantages:
- Sheets can be quite close to one another to

reduce concentration polarisation.


- Can be easily disassembled for cleaning and

replacement of defective membranes.


- Provides good flow control on both permeate

and feed side of the membrane.


- They have the ability to accommodate low

levels of suspended solids ad viscous fluids.

Disadvantages:
- Large number of spacer plates and seals are
required.
- Leakage through gaskets.
- Low packing density.
- Flow pattern and pressure drop distribution
are difficult to characterise.
- High module cost/expensive units.

Spiral wound:
- The spiral wound module is the next logical

step from a flat membrane.


- It is in fact a plate and frame system wrapped

around a central collection pipe.


- A permeate spacer is sandwiched between

two membranes.
- Feed flows through the feed spacer parallel to

the central tube, where as the permeate flows


through the permeate spacer, spirally
perpendicular to the feed flow direction.
- Spiral wound elements are most commonly
manufactured with flat sheet membrane of
either a cellulose diacetate and triacetate
blend or a thin film composite.

Advantages:
- They are compact; high membrane packing

density results in more efficient utilisation of


floor space.
- High pressure spiral elements can withstand

pressures in excess of 1000 psi.


- Low pressure drop and membrane
contamination .
- Minimum concentration polarisation.

Disadvantages:
- Difficult to disassemble and clean.
- Problems in handling suspended solids.
- It is not useful in high temperature
applications.
Tubular:
- Tubular module resembles a shell and tube

heat exchanger, but feed flows through the


tubes.
- Permeate passes through the wall of the tubes

into the shell side of the module and retentate


passes out through the other end of the tubes.
- Tubular module consists of parallel bundles of

rigid walled, porous or perforated tubes.


- Tubular membranes unlike hollow fibres are

not self supporting. Therefore these


membranes are kept inside a porous metallic,

ceramic or polymeric tube.

Advantages:
- Turbulent flow(providing good membrane-

feed contact and removing retentate film build


up)
- Relatively easy cleaning.
- Easy in handling suspended solids and viscous
fluids.
- Ability to replace or plug a failed tube while
the rest of the system runs.
- The feed flow pattern is easy to characterise
and therefore design and analysis based on
fluid dynamics principles is possible.

Disadvantages:
- Low packing density.
- High capital cost and pumping cost.
- Limited achievable concentration.

Hollow fibre:
- A perforated pipe is located in the centre of the

module through which the feed solution


enters.
- Here we have two different flow patterns i.e.

inside-out and outside-in.


- In inside-out, the feed solution is more

uniformly distributed throughout the module


so that the whole surface area is more
effectively used.
- In gas separation, the module will be of
outside-in type to avoid high pressure losses
inside the fibre and to attain a high membrane
area.

Advantages:
- Very high packing density.(4.5x106 fibres

inside a 25.4 cm diameter cartridge)


- Ease of cleaning using back flushing.
- Ability to achieve high concentration.
- Hollow fibre membranes can be designed for

recirculation and single pass operation.

Disadvantages:
- Fragility of fibre.
- Inability to handle suspended solids well.
- Channelling may occur in outside-in type

arrangement.
- The hollow fibre module could be used only

when the feed stream is relatively clean.


Flow pattern:
Ideally there are four different flow patterns for
membrane separation processes:
1) Perfect
mixing/complete mixing:
- Both the feed and
permeate sides of the
membrane are well mixed.
- It is similar to a continuous stirred-tank

reactor(CSTR).

2) Co-current flow:
- Here fluid on the feed

or retentate side flows


along and parallel to the upstream surface of
the membrane and permeate side fluid flows
on the downside
parallel to the retentate.

3) Countercurrent flow:
- Both the feed stream and permeate stream are

plug flow countercurrent


to each other.

4) cross flow:
- Feed stream is in plug flow and permeate
flows in a normal direction away from the
membrane.
Membrane materials:
There are large varieties of polymers which are
extensively used for
preparation of membranes. In general these
can be classified into three major
groups as follows:
1. Rubbery polymer:
When the polymer operates at a temperature
above the glass transition temperature (Tg), it is
called rubbery polymer. Their behaviour is
essentially that of a viscous liquid. In rubbery
polymers segmental motion of polymeric
molecules are rapid like liquid molecules. These
polymers have high fluxes of organics and low
flux of water. Silicone rubber, Polydimethyl
siloxane, polyvinylammonium thiocyanate, etc.
are the examples of rubbery polymers.

2.Glassy polymer:
When the polymer operates at a temperature
lower than the glass transition temperature (T),
it is known as glassy polymer. These polymers
are either amorphous or crystalline. Segmental
motion or rotation of polymeric molecules is
restricted leading to heterogeneity of polymer
structure. Polycarbonate, cellulose acetate,
polysulphone, etc. are the examples of glassy
polymers.

3. Lon exchange polymer:


Ion exchange membranes are essentially ion
exchange resins made in membrane form.
These are having ionic charges on the
polymeric segment. A negatively charged
membrane is permeable only to cations, and
therefore, is called a cationic membrane.
Similarly, when the membrane is positively
charged, it is permeable to anions and is called
an anionic membrane. Ion exchange
membranes are very selective for water.

Some of the polymers that are widely used as


potential membrane materials
are discussed in the following:
Cellulose derivatives:
The high structural regularity and
intermolecular hydrogen bonding of its
hydroxyl groups make cellulose difficult to
dissolve. They show pronounced
hydrophilicity, which is very useful in
minimizing fouling of the membrane. One of the
important advantages of CA membrane is that
these are available with wide range of pore
sizes with reasonably high fluxes. However, CA
membrane suffers from certain disadvantages
also. These include narrow temperature range
(30°C to 40°C), low pH range (pH 3 to pH 6) and
poor resistance to chlorine. Another limitation
of cellulose derivatives is borderline glass
transition temperature (68.6°C) which limits its
utility at elevated temperatures and pressures.

Aromatic polyamides:
Aromatic polyamides (also called aramides) are
highly melting (275°C) crystalline polymers
with better thermal stability. They are
prepared either by the self condensation of
aromatic amino acids or by the
polycondensation between aromatic diacid
chlorides and aromatic diamines. These are
characterised by having an amide (-CONH-)
bond in its structure. Polyamide (PA)
membranes can overcome some of the
drawback of CA membrane. These have higher
pH tolerance. However, PA membranes are
worse than CA in terms of chlorine tolerance
due to electrophilic substitution of aromatic
rings by chlorine which disrupt intermolecular
hydrogen bonding resulting in increased
permeability and reduced selectivity.

Polysulphone:
Polysulphone is a condensation product of
bisphenol-A and dichlorodiphenyl sulfone.
Polysulphones (PS) and polyether sulphones
(PES) are having high degree of molecular
immobility, high rigidity, creep resistance and
dimensional stability. Their salient features
include wide range of operating temperature
(up to 75°C for PS and up to 125°C for PES),
wide pH tolerance (pH 1 to pH 10), and fairly
good chlorine resistance.

Polyimides:
Polyimides are extensively investigated as
candidate polymer for reverse osmosis
membranes. Polyimides are obtained by
reaction of diamines with dianhydrides and
subsequent condensation of the resultant
polyamic acid. Because of the supposed
absence of-NH-groups in their backbones, it
was initially felt that polyimides would be
resistant to oxidation by chlorine. However, the
chlorine resistance of polyimides has proven, in
the long run, to be inadequate and the interest
in polyimide reverse osmosis membranes has
subsided. Present activity in polyimide
membrane polymers centres around their use
in gas separation membranes.

Interfacially synthesized polymers:


The high melting temperatures of aromatic
polyamides and related polymers required
their synthesis by interfacial or low
temperature polycondensation techniques.
Interfacial polycondensation is unusual in that
neither monomer purity nor exact
stoichiometry of reagents is required and can
be adopted for direct synthesis of the films in
situ over a microporous support. This
technique is utilized commercially for the
preparation of polyurea, polyamide (PA 300)
and crosslinked aromatic polyamide (FT 30)
membranes. In each case, a microporous
polysulphone membrane with surface pores of
< 0.1 um size was first wetted with a dilute
aqueous solution of the water soluble
component like polyethyleneimine (PEI) or
meta-phenylenediamine and interfacially
reacted with hexane solutions of toluene
diisocyanate (TDI), isophthaloyl chloride or
trimesoyl chloride. As compared to asymmetric
membranes, interfacially synthesized
membranes provide high permeability rates
without sacrificing selectivity.
Polytetrafluoroethylene (PTFE):
Polytetrafluoroethylene (PTFE), also known as
Teflon, in trade, may be visualized as
polyethylene with all its hydrogen atoms
substituted by fluorine. The monomer
tetrafluoroethylene (TFE) is produced by
dechlorination of dichloro tetrafluoroethane or
by the decarboxylation of sodium perfluoro-
propionate. PTFE is a straight chain, highly
crystalline polymer with a very high degree of
polymerization of the order of 100,000, which
gives it considerable strength. It is also very
stable to strong acids, alkalis and solvents and
can be used at a wide range of temperature
from -100°C to 260°C. It is made by a
combination of heating and stretching melted
films. It is extremely hydrophobic and finds
many uses in the treatment of organic feed
solutions vapours and gases.

Polycarbonate:
The commercial aromatic polycarbonates (PC)
are a class polyesters derived from carbonic
acid and bisphenol-A. Polycarbonates are
characterised by the presence of the -OCOO-
group in the chain. They are mainly amorphous
in structure. Thin dense films (~ 10 um) of high
molecular weight PC are the most common
substrate for the preparation of microporous
radiation track membranes. The non planner
configuration of the polycarbonates provides a
large average interchain displacement in the
membrane with the result that gas permeability
is much higher through PC films.
Polycarbonates differ from most other
amorphous polymers in that they possess
ductility and toughness below T. Since
polycarbonates are thermoplastic, they can be
extruded into various shapes, including films
and sheets. Polycarbonates are often
investigated for preparing block copolymers
with polyethylene glycols (PEG) and silicones.
Copolymers of PC and PEG are known to be
suitable for making hemodialysis membranes.
Block copolymers of PC with silicone combine
the excellent film forming properties of PC and
gas separation properties of silicone. Both flat
sheet and hollow fibre membranes of silicone
polycarbonate copolymers are investigated for
use in membrane blood oxygenators.

Polypropylene:
Polypropylene is produced by the
polymerization of propylene using the famous
Ziegler-Natta catalysts. The typical
polymerization catalysts are Al(iso-C,H,), and
TiCl,, or Al(C,H,), and TiCl: Polypropylene can be
made by thermal inversion process and also by
the melt-extruding and stretching. It is usually
available in the form of hollow fibres. They are
hydrophobic, relatively inert, and can
withstand moderately high temperatures.

Inorganic membrane materials:


The application of polymer membranes is
generally limited to temperatures below about
200°C and to the separation of mixtures that
are chemically inert. Most inorganic membrane
materials have much better selectivity and
permeability (at high temperatures) than
polymeric membranes (at low temperature),
with data points falling beyond the Robeson
boundary lime" for most gas pairs. A large
number of materials (from alpha alumina to
zircon) are available for the manufacture of
ceramic membranes. The most common
membranes are made of Al, Si, Ti or Zr oxides,
with Ti and Si being more stable than Al or Si
oxides. In some less frequent cases, Sn or Hf are
used as base elements. Each oxide has a
different surface charge in solution. Other
membranes can be composed of mixed oxides
of two of the previous elements, or are
established by some additional compounds
present in minor concentration. Ceramic
membranes are available form several
manufacturers in different shapes, mainly
round and hexagonal, and with various channel
diameters.
CHAPTER 3: REVERSE OSMOSIS

Reverse osmosis (RO), less commonly known


as hyperfiltration, is a high pressure, energy
efficient technique for de watering process
streams, concentrating low molecular weight
substances in solution, or purifying
wastewater. It has. the ability to concentrate
dissolved as well as suspended solids. RO is
widely used in the desalination of brackish
water. To desalinate water, it is required to
create a flow through a membrane, causing the
water to leave the salty side of the membrane,
passing into the unsalted side. To achieve this,
pressure must be created upon the water
column on the salt side of the membrane;
firstly, to remove the natural osmotic pressure
and secondly, to create extra pressure on the
water column in order to push the water
through the membrane. As the name suggests,
reverse osmosis is osmosis in reverse.
Therefore, to describe reverse
osmosis, it is first necessary to understand the
phenomenon of osmosis.
Concept of osmosis:
The word 'osmosis' is originated from the
Greek word osmos which means "to push'.
Osmosis is a natural phenomenon, most
commonly observed in plants. If we do not
water our plants they wilt. A plant cell is a
semipermeable (water flows through the
membrane but salts do not) membrane with the
living stuff inside in a salt solution. Water is
drawn into the cell from outside because pure
water moves across a semipermeable
membrane to dilute the higher concentration of
salt inside. This is how water is drawn in from
the ground when we water our plants. On the
other hand, if we add salt to plants (over
fertilise or spill some salt on the grass), the
plant wilts because the salt concentration
outside of the cell becomes higher than inside
and then water moves across the membrane
from inside to outside.
Osmosis may be defined as the physical
movement of a solvent through a
semipermeable membrane based on a
difference in chemical potential between two
solutions separated by that semipermeable
membrane. Let us take a simple example to
demonstrate osmosis. A beaker of water as
shown in Figure 3.1 is divided through the
centre by a semipermeable membrane. The
thick dotted line represents the semipermeable
membrane. We will define this semipermeable
membrane as lacking the capacity to diffuse
anything other than the solvent, in this case
water molecules. Now, if we add a small amount
of common salt (NaCI) to the solution on one
side of the membrane, the salt water solution
will be having a higher chemical potential than
the water solution on the other side of the
membrane. Therefore, in an effort to
equilibrate the difference in chemical potential,
water begins to diffuse through the membrane
from the water side to the salt water side. This
movement is osmosis. The pressure exerted by
this mass transfer is known as osmotic
pressure.
The diffusion of water will continue until one of
the two constraints is met. One constraint
would be that the solutions essentially
equilibrate, at least to the extent that the
remaining difference in chemical potential is
offset by the resistance or pressure loss of
diffusion through the membrane. The other
constraint is that the rising column of salt water
exerts sufficient hydrostatic pressure to limit
further diffusion. By observation, then, we can
measure the osmotic pressure of a solution by
noting the point at which the head pressure
impedes further diffusion.

Determination of Osmotic Pressure:


The thermal movement of a solute molecule
within a solvent is overdampened by the
solvent molecules that surround it. The solute
movement is wholly determined by
fluctuations of thermal collisions with nearby
solvent molecules. However, the average
thermal velocity of the solute molecule is the
same had it been free in a gas phase, without
nearby solvent molecules. Whenever a solute
movement is blocked by the membrane it will
transfer momentum to it and, therefore,
generate pressure on it. Since the velocity is the
same as that of a free molecule, the pressure
will be the same as the pressure of an ideal gas
of the same molecular concentration. Hence,
the osmotic pressure I, is given by the Van't Hoff
formula, which is identical to the pressure
formula of an ideal gas:
where n is the number of kg mol of solute, I the
molar volume of pure solvent water in m'
associated with n kg mol of solute, R is the gas
constant (82.057 × 10ª m' atm/kg mol K, and T
is the absolute temperature in K. The osmotic
pressure does not depend on the solute type, or
its molecular size, but only on its molar
concentration, as the formula states. Figure 3.3
shows connected vessels separated by a
semipermeable membrane. If there is only
water in the device, the level will be the same at
both arms. When solute molecules are added to
one arm. water will start to flow into it, so that
its level will rise at this arm, and fall at the other
arm. Figure 3.3

The system will stabilise when the osmotic


pressure is balanced by the hydrostatic
pressure generated by the difference h in the
water levels. This can be given by the following
expression: cRT = ph
where p is the specific gravity of water. The
physical significance of osmotic pressure is well
known in biological and clinical situations.
Germination of seeds to burst open their
protective layer, transportation of water from
the soil to the root system in plants and
activation of dormant cells in a solution of
lower osmotic pressure are all due to the
difference of osmotic pressure. Even relatively
small concentrations of dissolved solutes can
develop fairly large osmotic pressures. Table
3.1 shows osmotic pressure of various dilute
aqueous solutions of NaCl at 25°C.

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