Advances in

Separation
Science

UNIT 1
Reference books

– Separation process principles by Seader and Henly- Wiley

– Separation processes by C. Judson King- McGrawHill
– The structure of separation processes
– Definition of separation and separative work
– Characterization of concentration distribution
– Morphology of Separation processes
Introduction

– Separation processes are integral part

– If we consider a reactive system, where, certain products are of primary
interest, separation units are either put in the upstream or downstream.
– It may happen that the reactants are gaseous and should be devoid of moisture.
In such cases, a separation unit must be present as an upstream unit.
– On the other hand, if a particular product is kept in mind, a separation unit
must be placed at the downstream
– There may be processes, where, the separation is the only objective.
– For example, if we consider a treatment process of an industrial effluent
 Introduction

– In an effluent treatment process, there are three steps, namely, primary, secondary and
tertiary treatment processes.
– Primary treatment processes include coagulation, flocculation, etc.
– Secondary treatment processes are mainly oxidation ponds, etc.
– Tertiary treatment processes involve adsorption, membrane separation, etc.
– In food and juice processing industries, separations are primary stages of operation.
– Most of the pharmaceutical industries have separation units as integral parts in the
downstream or they are the main units.
– In milk processing separation processes are primary.
– Most of the separation processes involve, either separation of solutes from the solvent or,
separation of a mixture of solutes.
Introduction

– In order to effect separation, one has to put either energy or an extra material from
outside to disturb stability.
– This is equivalent to the concept of exceeding the activation energy of separation by an
external agent (agent may be energy or matter)
– 1) Separation of salt from sea water.
– (a) supply heat and boil water off, condensing the water at a lower temperature;
– (b) supply refrigeration and freeze out pure ice, which we can then melt at a higher
temperature;
– (c) pump the water to a higher pressure and force it through a thin solid membrane that
will let water through preferentially to salt.
Introduction

– 2) Separation of charged colloidal particles which are stable in a solution. A

coagulant, like potassium alum or ferric chloride or calcium oxide (selection
depends upon the operating pH) is added.
– These coagulants are generally of opposite charges of the colloids.
– These colloids get themselves attached to the coagulants by electrostatic
attractive forces and the whole assembly becomes heavier and settles down.
Schematic of Separation Process
Inherent Separation Factor

– The extent of separation is defined by inherent separation factor.

– Inherent Separation factor between two species ‘i’ and ‘j is defined as
– =

– Where, 1 and 2 are two streams

Inherent Separation Factor

– =1, no separation occurs

– is less than 1, stream ‘1’ is concentrated in ‘j’ and stream ‘2’ is concentrated in
‘i’
– is more than 1, stream ‘1’ is concentrated in ‘i’ and stream ‘2’ is concentrated
in ‘j’
Classification

– The separation processes are divided into two categories

– Equilibrium governed separation processes and
– Rate governed separation processes.
Classification

– In equilibrium governed separation processes, the product phases are in

equilibrium with the inlet phases.
– Distillation, absorption etc. are examples of equilibrium governed separation
processes
– In rate governed separation processes, product phase composition or
separation occurs due to the difference of rate of physical transport of species
alone.
– Membrane based processes are rate governed separation process
CANE SUGAR REFINING

– Common white granulated sugar is typically 99.9 percent sucrose and is one of
the purest of all substances produced from natural materials in such large
quantity.
– Sugar is obtained from both sugar cane and sugar beets
Cane Sugar Refining

– Cane sugar is normally produced in two major blocks of processing operations

– Preliminary processing takes place near where the sugar cane is having typically
following basic steps
– 1. Washing and milling.
– 2. Clarification.
– 3. Evaporation, crystallization, and centrifugation.

(Gerstner, 1969; Shreve and Brink, 1977, pp. 506-523).

1. Washing and milling

– The sugar cane is washed with jets of water to free it from any field debris and
is then chopped into short sections.
– These sections are passed through high-pressure rollers which squeeze sugar-
laden juice out of the plant cells.
– Some water is added toward the end of the milling to leach out the last
portions of available sugar.
– The remaining cane pulp. known as bagasse, is used for fuel or for the
manufacture of insulating fiberboard
2. Clarification

– Milk of lime, Ca(OH)2 ,is added to the sugar-laden juice, which is then heated.
– The juice next enters large holding vessels, in which coagulated colloidal
material and insoluble calcium salts are settled out.
– The scum withdrawn from the bottom of the clarifier is filtered to reclaim
additional juice, which is recycled.
3. Evaporation, Crystallization &
centrifugation
– The clarified juices are then sent to steam-heated evaporators, which boil off much of
the water, leaving a dark solution containing about 65% sucrose by weight.
– This solution is then boiled in vacuum vessels.
– Sufficient water is removed through boiling for the solubility limit of sucrose to be
surpassed, and as a result sugar crystals form
– The sugar crystals are removed from the supernatant liquid by centrifuges.
– The liquid product, known as blackstrap molasses, is used mainly as a component of
cattle feed.
– The solid sugar product obtained from this operation contains about 97% sucrose,
and is often shipped closer to the point of actual consumption for further processing
Cane Sugar Refining Manufacture

– As a first step, the raw sugar crystals are mixed with recycle syrup in minglers so as to
soften the film of molasses adhering to the crystals.
– This syrup is removed in centrifuge and is both recycled and processed for further
sugar recovery.
– The sugar crystals (now at a sugar content of 99%) are next dissolved in hot water and
treated (in vessels called blowups) with calcium hydroxide and phosphoric acid to
precipitate foreign substances which form insoluble compounds with these chemicals.
– Diatomaceous earth, a spongy porous material, added as a filter aid, serves to provide
an extensive amount of solid surface, which facilitates the removal of insolubles in the
filtration step that follows
Sugar refining

– The sugar syrup is next passed slowly through large beds of granular animal derived
charcoal (boneblack, or char).
– Purpose: To adsorb color-causing substances and other remaining impurities onto the
surface of the char.
– The sugar solution is then freed of excess water by boiling in steam-heated
evaporators, or vacuum pans
– Again, sufficient water is boiled of to cause the solubility limit of sucrose to be
exceeded, and crystals of pure sugar form, leaving essentially all remaining impurities
behind in the solution, which is recycled to appropriate earlier points in the process
– The recycle solution is removed from the pure sugar crystals in large centrifuges
Sugar refining

– Before packaging, the sugar crystals must be dried

– This is accomplished by tumbling the crystals through a stream of warm air of
low humidity in large, slightly inclined, horizontal revolving cylinders called
granulators.
– The sugar granules falling off short shelves attached to the rotating wall which
serve to distribute the sugar in the warm air.
– After drying, the sugar is passed through a succession of screens of different
mesh sizes to segregate crystals of different sizes (fine. coarse, etc.)
Cane sugar manufacture
– There are 11 different classes of separation processes in manufacturing and refining of cane
sugar
– 1. Settling (clarifiers)
– 2. Filtration (scum filter, pressure filters)
– 3. Centrifugation (raw-sugar centrifuges, white-sugar centrifugals)
– 4. Screening (classification by crystal Size)
– 5. Expression (milling rolls)
– 6. Washing and leaching (debris removal, water addition to milling rolls, minglers)
– 7. Precipitation (lime tanks, blowups)
– 8. Evaporation (evaporators, vacuum pans)
– 9. Crystallization (vacuum pans)
– 10. Adsorption (char filters)
– 11. Drying (granulators)
Chemical potential in interfacial mass
transfer
– A species of molecules is said to be in equilibrium when there does not exist a
chemical potential gradient across the boundaries of the system.
– Chemical potential (μ) of a system is defined as the amount of change of energy
on introduction of a new species in the system keeping the entropy and volume
unchanged.
– Typically the partial molar Gibbs energy is referred as the chemical potential of
the system. In the absence of any external force field, the total energy change
of the system is
Chemical potential in interfacial mass
transfer
 Chemical potential in interfacial mass
transfer
– At equilibrium, for a constant temperature and pressure, μ of each of the species are constant and
equal.
– Mass transfer is inherently a non-equilibrium process, characterized by the net motion of molecules
down a chemical potential gradient (concentration gradient).
– The mass transfer often takes place across an interface between the two phases. At the interface
between two phases, the chemical potential of the diffusing components of the two phases are
equal to each other.
– The energy changes in mass transfer processes include internal entropy, volume and interfacial
changes, which occur simultaneously and as a result of the mass transfer.
– In mass transfer processes, the molar or mass potential provides the total energy density change, i.e.
per mole or per unit mass.
– Thus, at equilibrium, it is this total energy density that must be constant, whereas in non-equilibrium
systems its gradient provides a driving force for mass transfer.
Use of Navier Stokes equation in
mass transfer
– Separation should occur under a steady state conditions.
– Feed and Product phases flow past each other.
– In almost all the cases, the flow directions of the two phases are countercurrent
in nature in order to have the higher driving force.
– The interface (in case of equilibrium governed separations) or interphase (in
case of rate governed) between the two flowing streams dictates the mass
transfer of the species either through the equilibrium relations or transport
laws through the interphase
– In order to get an idea the variation of solute concentration in the bulk phases,
the coupled mass transfer and velocity field have to be solved in conjunction.
 Use of Navier Stokes equation in
mass transfer
– The velocity field is characterized by equations of motion or Navier Stokes equation and
the concentration field (mass transfer) is denoted by solute balance equation in its
differential form.
– Since, the solute balance equation contains, the convective terms, it is coupled with the
velocity field.
– Therefore, the simultaneous solution of these would result the concentration field of the
solute to be separated in the feed side.
– After that, the concentration field is evaluated at the interface and its value is evaluated in
the other phase by using the equilibrium relation (in case of equilibrium governed
processes) or transport law through the interphase (in case of rate governed processes)
– The bulk concentration profile of the target or other phase is then obtained by
simultaneous solution of velocity and concentration field in that phase
 Equilibrium governed processes

– Four popular and quite common equilibrium governed separation processes are described.
– Distillation is based on the differences in boiling points of the constituents in a mixture
– In this process, external heating is required to heat up the system
– Top vapor phase is condensed and is rich in one component and the residual liquid phase is rich
in other component. This is known as flash distillation.
– In another process, a part of the condensed stream from the top is recycled down the column.
This is known as reflux.
– In this case, there is intimate mixing of the liquid stream coming down and vapor going up. This
operation is carried out in counter current fashion and this enhances the efficiency of the
process.
– This is generally used for separation of aqueous mixture of various organic solvents, like,
toluene, benzene, acetone, ethyl benzene, etc.
Equilibrium governed processes

– Absorption
– Vapor in an inert gas is absorbed in a liquid stream, The vapor is soluble in the liquid.
– The liquid stream rich in solubilized vapor components is separated by distillation or some
other suitable techniques.
– The liquid can be recovered and reused in the process itself.
– Typically this operation is carried out in counter current manner to enhance the efficiency of
this process.
– Sometimes, the packed beds or staged beds like trays are used to have better mixing during
the transfer process.
– Bulk phenomena, i.e., the gaseous solutes are transported to the bulk of the liquid stream.
– To effect separation, a matter is introduced in the system.
Equilibrium governed processes

– Adsorption
– Separation of solutes by transporting it from gaseous or liquid streams on a
solid surface is known as adsorption.
– Surface phenomenon: The solute is fixed on the solid surface only
– Typically, the solid surface is specific for a particular component present in the
feed stream.
– Typically, in a bed, the adsorbent particles are kept and the fluid is pumped
through the system for intimate mixing.
– In the process, the solute is transferred to the solid phase.
– To effect separation, a matter is introduced in the system.
Equilibrium governed processes

– Drying
– Water vapors from a solid material are removed by using a vapor stream to an
acceptable small limit
– Carried out by applying thermal energy
– The process efficiency depends on the temperature, relative humidity and other
thermo physical properties of the drying vapor as well as the temperature and
other thermo-physical properties of the solid.
Rate governed processes

– Most of the membrane based processes are the rate governed.

– The main crux of the separation lies in the difference of transport of various
species through the membrane.
– The driving force of such transport is generally gradient of chemical potential.
– Gradient of chemical potential: Concentration gradient, Pressure gradient,
Temperature gradient and Electrochemical Potential gradient.
– Presence of these causes (one or more of such gradients) results into effects
(the difference in separation and hence effects)
Rate governed processes

– Osmosis is observed when a solution is separated from the solvent by a semipermeable (only
solvent is permeable species) membrane.
– Difference in osmotic pressure across the membrane causes the transport of the solvent
– Osmotic pressure is a colligative property
– The concentration (or more generally activity) gradient of the solvent is the main driving force in
osmosis
– In this case, the solvent flows from the solvent side to the solution side until, the solvent activity
becomes almost equal in both the sides.
– This results in generation of hydrostatic pressure difference between the two sides, known as
osmotic pressure.
– If the initial concentration of solute is more in the solution side, more solvent will flow in from
the solvent side to equalize the solvent activity on both the sides, resulting in more osmotic
pressure difference.
 Rate governed processes

– Reverse Osmosis
– Pressure is applied on the solution side externally (using a pump or a compressor),
so that the osmotic pressure is overcome and the solvents are forced out of the
solution side
– The efficiency of this process depends on the porosity, morphology and thickness
of the membrane.
– These factors influence the transport of the solvent through the membrane
immensely and thereby, dictating the throughput of the process and the quality of
the product.
Rate governed processes

– Membranes have very small pore size: used for separation of lower molecular
weight species, like, salts.
– A salt having very high osmotic pressure, the operating pressure in the feed side
of a reverse osmosis process is therefore extremely high. This will lead to
deposition of salts near the membrane surface, leading to build up of a
concentration boundary layer. Therefore, the pressure gradient in this system
leads to concentration difference.
Rate governed processes

– Dialysis
– Two liquid streams are separated by a permeable barrier or membrane
– In the feed side, a specific set of solutes are permeated through the membrane to the
other side.
– The upstream feed is known as the feed side and the downstream is known as the
dialysate.
– Typically, dialysate stream is pure distilled water.
– Thus, the concentration gradient between the two streams is the maximum.
– The transport is effected by the concentration gradient between two streams.
– The duration of separation entirely depends on the rate of the solutes through the
membrane.
Novel separation processes

– The separation processes those are not conventional and routine fall under this
category.
– Therefore, some of the equilibrium and rate governed separation processes are
included this.
– Some of the processes are identified as, (i) Membrane based separation
processes; (ii) Chromatographic separation processes; (iii) Electric field assisted
separation processes; (iv) Ion exchange processes, etc.
Settling

– A suspension of solids in a liquid is held in a tank until the solids settle to the
bottom to form a thick slurry or scum.
– Solids-free liquid is withdrawn from the top of the vessel. This process requires
that the solids be denser than the liquid
Filtration

– A solid-in-liquid suspension is made to flow through a filter medium such as a

fine mesh or a woven cloth.
– The pores of the filter medium are so small that the liquid can pass through but
the solid particles cannot.
– Sometimes a filter aid (diatomaceous earth) is added to form a stiII more
effective filter medium on top of the mesh or cloth.
– Filtration is a separation based on size, whereas setlling, is a separation based
on density
Centrifugation

– A solid-in-liquid suspension is whirled rapidly.

– The centrifugal force from the rotation aids the phase separations.
– Centrifuges may operate on a settling principle, wherein the denser phase is
brought to the outs)de by the centrifugal force, or on filtration principle, as in a
basket centrifuge. where the mesh of the basket retains solid particles and the
centrifugal force causes the liquid to now through the solids in the basket more
readily than in an ordinary filter
Screening

– Particles are shaken on a screen.

– The smaller particles pass through the screen, and the larger particles are
retained