USES AND

CHARACTERISTICS OF
SEPARATION
PROCESSES
CHAPTER ONE
When salt is placed in water, it dissolves and tends to form a solution of uniform
composition throughout. There is no simple way to separate the salt and the water
again.

 This tendency of substances to mix together intimately and spontaneously is a

manifestation of the second law of thermodynamics: WHICH STATES THAT ALL NATURAL
PROCESSES TAKE PLACE SO AS TO INCREASE THE ENTROPY, OR RANDOMNESS,
OF THE UNIVERSE.

In order to separate a mixture of species into products of different composition we must
create some sort of device, system, or process which will supply the equivalent of
thermodynamic work to the mixture in such a way as to cause the separation to
occur.
For example, if we want to separate a solution of salt and water,
we can

supply heat and boil water off, condensing the water at a lower
temperature.
supply refrigeration and freeze out pure ice, which we can then melt at a
higher
temperature.
pump the water to a higher pressure and force it through a thin solid
membrane that will let water through preferentially to salt.

All three of these approaches (and numerous others) have been under
active study and development for producing fresh water from the sea.
“We shall define separation processes as those
operations which transform a mixture of substances
into two or more products which differ from each other
in composition”.

The many different kinds of separation process in use and their

importance to mankind should become apparent from the following two examples,
which concern basic human wants, food and clothing.
AN EXAMPLE: 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 is normally produced in two major blocks of processing operations.
Preliminary processing takes place near where the sugar cane is grown (Hawaii,
Puerto Rico, etc.) and typically consists of the following basic steps, shown:

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.
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.
EVAPORATION, CRYSTALLIZATION, AND 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.
Before packaging for sale, the sugar crystals must be dried, since they still
contain about 1 % water. 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 interior of a granulator, 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.).
There are 1 1 different classes of separation processes
included in the steps shown

Settling (clarifiers):
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 (scum filter, pressure filters).
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 still more effective filter
medium on top of the mesh or cloth.
Filtration is a separation based on size, whereas settling is a separation based on
density.
centrifugation (raw-sugar centrifuges, white-sugar centrifugals).

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 outside by the centrifugal force, or on a filtration principle, as in a basket centrifuge,
where the mesh of the basket retains solid particles and the centrifugal force causes
the liquid to flow through the solids in the basket more readily than in an ordinary filter.
Screening (classification by crystal size).
Particles are shaken on a screen. The smaller particles pass through the screen, and
the larger particles are retained.

Expression (milling rolls).

Mechanical force is used to squeeze a liquid out of a substance containing both solid
and liquid.
Washing and leaching (debris removal, water addition to milling rolls,
minglers).
Soluble material is removed from a mixture of solids by dissolution into a solvent liquid.

Precipitation (lime tanks, blowups).

A chemical reactant is added to a liquid solution causing some, but not all, of the
substances in solution to form new insoluble compounds.
Evaporation (evaporators, vacuum pans).
Heat is added to a liquid containing nonvolatile solutes in a volatile solvent. The solvent
is boiled away, leaving a more concentrated solution. Solvent can be recovered by
condensing the vapor.

Crystallization (vacuum pans).

A liquid is cooled and/or concentrated so as to cause the formation of an equilibrium
solid phase with a composition different from that of the liquid.
Adsorption (char filters).
Trace impurities in a fluid phase are retained preferentially on the surface of a solid
phase, being held there by van der Waals forces (physical adsorption) or chemical bonds
(chemical adsorption).

Drying (granulators).
Water is caused to evaporate from a solid substance by the addition of heat and the
circulation of an inert-gas stream of low humidity.
EXAMPLE: MANUFACTURE OF p-
XYLENE
p-Xylene is an important petrochemical which is an intermediate for the manufacture of
terephthalic acid, HOOCC6H4COOH, and dimethyl terephthalate, CH3OOCC6H4COOCH3 ,
both of which are raw materials for the manufacture of polyester fibers (Dacron, etc.)
p-Xylene is one of the three xylene isomers:
a primary distillation step, separates crude oil into various streams boiling at different
temperatures.
The naphtha feed for the xylene manufacture process is typically a stream boiling
between 120 and 230 K.
 The naphtha is charged to a high-temperature high-pressure chemical reactor system
called a reformer, where reactions convert much of the largely paraffin naphtha into
aromatic molecules.

Typical reactions include cyclization, i.e., conversion of n-hexane into cyclohexane, etc.,
CONVERSION OF N-HEXANE INTO CYCLOHEXANE, ETC.,
aromatization, i.e., conversion to cyclohexane into benzene
plus hydrogen, etc.,
The product aromatics are a mixture of benzene, toluene, the xylene isomers, and
higher aromatics.

The catalyst for the reformer must be protected against deactivation by a hydrogen
atmosphere.

Since hydrogen is costly, it is recovered in a vapor liquid separator for recycle.

A bleed stream taken off from the recycle gas is necessary in order to remove the net
amount of hydrogen formed in the cyclization and aromatization reactions.
In order to obtain an optimal product distribution pattern from the reforming reaction,
the reaction is usually carried out in a series of catalyst beds, each operating at a
different temperature.
Most of the output from an oil refinery reforming unit like this becomes high octane
gasoline, but the product stream is also suitable for the production of xylenes and other
aromatics.

for p-xylene manufacture a portion of the effluent from the separator passes to a
distillation tower, which removes butane and lighter molecules.

The remaining material passes to a liquid-liquid extraction process, in which the

hydrocarbon stream is contacted with an immiscible stream of a solvent, such as
diethylene glycol. The aromatics dissolve preferentially in the solvent, while the
paraffins and naphthenes (cyclic nonaromatics) do not
One type of device for carrying out extraction process consists four rotating-disk
contactors, which are large vessels containing a number of horizontal disks mounted on
a vertical motor-driven stirrer shaft.
These rotating disks agitate the two immiscible liquid phases (hydrocarbon and solvent)
inside the vessels and thus promote a high rate of dissolution of the aromatics into the
solvent phase.
The aromatic-laden solvent stream passes to a distillation tower, which separates the
aromatics from the solvent. The solvent is then recycled to the extraction step.
The distillation tower for separating the aromatics from the solvent is located behind
the rotating-disk contactors
Two more distillation towers follow the extraction step:
1. removing benzene and toluene from the xylenes and heavier aromatics
2. removing the heavier aromatics from the xylenes.

At this point there is a stream of mixed xylene isomers, which is next chilled below the
freezing point.

The resultant crystals are composed of p-xylene; hence removal of crystals through
centrifugation or filtration accomplishes a separation of the para isomer from the ortho
and meta isomers.
The p-xylene is melted and taken as product, while the supernatant liquid is sent to an
isomerization reactor which provides an equilibrium mix of all three xylene isomers.

Again there is a solid catalyst in the reactor which must be protected by a high-pressure
circulating hydrogen stream.

The equilibrium xylene mix is recycled to the crystallizer, and in this way essentially the
entire xylene cut is converted into p-xylene product.
n practice, the p-xylene manufacture process probably would be part of a much larger
installation, most likely of a petroleum refinery manufacturing several different gasoline
streams, one of which would be a major portion of the total reformer effluent.

The aromatics facility might also be larger, including provision for additional products of
benzene, toluene, o-xylene, etc., all of which are large-volume petrochemicals. There
might also be a hydrodealkylation facility for converting toluene into benzene.
FOUR DIFFERENT CLASSES OF SEPARATION PROCESS ARE
COVERED IN AROMATIZATION
Vapor-liquid separation (hydrogen recovery).
A multiphase stream is allowed to separate into vapor and liquid phases of different
compositions, each of which is removed individually. In some cases heating (evaporation)
or pressure reduction (expansion) may be necessary to cause the formation of vapor.
Distillation (dehutanizer, regenerator, toluene- xylene splitter, xylene
recovery).
This is a separation based upon differences in boiling points, obtained by repeated
vaporization and condensation steps.
Extraction (preferential dissolution of aromatics into glycol).
Two immiscible liquid phases are brought into contact, and the substances to be
separated dissolve to different extents in the different phases.

Crystallization (p-xylene recovery).

A solid phase is formed by partial freezing of a liquid,and the two resulting phases have
different compositions.
IMPORTANCE AND VARIETY OF SEPARATIONS

The separation sequence presented in the p-xylene manufacture example is

representative of processes which are based upon chemical reactions.
The reactor effluent is necessarily a mixture of chemical compounds: the desired
product, side products,unconverted reactants, and possibly the reaction catalyst.
Typically, the desired product must be separated from this mix in relatively pure form,
and the unconverted reactants and any catalyst should be recovered for recycle.
All the reactants may have to be prepurified. Separation processes of some sort are
required for these purposes.Separation equipment accounts for 50 to 90% of the capital
investment in large-scale petroleum and petrochemical processes centered around
chemical reactions.
Water and air pollution present separation problems of immense social importance.
Indeed, water and air pollution are striking examples of the point made earlier that
naturally occurring processes are mixing processes.

As water is used for various purposes, it picks up undesirable solutes which
contaminate it. Similarly, noxious substances emitted into the atmosphere quickly
spread throughout the atmosphere and cause smog and related problems.

A number of different separation processes may be used for the removal of

contaminants in waste air and water effluents.
Alternatively, a separation process may be employed at an earlier point, e.g., for the
removal of sulfur from fuel oils before combustion

Separations also play an important role in schemes to reprocess solid wastes, such as
municipal refuse (Mallan,1976).
The story of the Manhattan Project of World War II is to a major extent a story of efforts
to develop a process and construct a plant for the separation of fissionable 235U from
the more abundant 238U (Smythe, 1945; Love, 1973).

Thermal diffusion, gaseous diffusion, gas centrifuges, and electromagnetic separation

by a scheme similar to the mass spectrometer (in a device known as the calutron, after
the University of California) were all investigated along with other approaches ; gaseous
diffusion ultimately was the most successful process.
a prime example of a separation problem of current importance is the desalination of seawater in
an economical fashion.
Processes considered on research, development, and production scales(Spiegler, 1962) include:
1. evaporation through heating
2. evaporation through pressure reduction
3. freezing to form ice crystals
4. formation of solid salt-free clathrate compounds with hydrocarbons
5. electrodialysis, reverse osmosis
6. precipitation of the solids content by elevation to a temperature and pressure above the critical
point, preferential extraction of the water into phenol or triethylamine, and ion exchange.
ECONOMIC SIGNIFICANCE OF SEPARATION PROCESSES

Often the need for

separation
processes accounts
for most of the cost
of a pure substance.
In the figure there is a roughly inverse proportion between the market prices of a number of
widely varied commodities and their concentrations in the mixtures in which they are found.

This relationship reflects the need for processing a large amount of extra material when the
desired substance is available only in low concentration.

There is also a thermodynamic basis for such a relationship, since the minimum isothermal
work of separation for a pure species is proportional to:
— In a, , where a, is the activity of the species in the feed mixture. The activity, in turn,is
roughly proportional to the concentration.
It will become apparent that distillation is the most prominent separation process used
in petroleum refining and petrochemical manufacture.

Zuiderweg(1973) has estimated that the total investment for distillation equipment for
such applications over the 20 years from 1950 to 1970 was $2.7 billion, representing a
savings of $2.0 billion dollars over what would have been the cost if there had been no
improvement in distillation technology over that 20-year period.
CHARACTERISTICS OF SEPARATION PROCESSES

Separating Agent
The feed may consist of one stream of matter or of several streams.
There must be at least two product streams which differ in composition from each
other; this follows from the fundamental nature of a separation.
The separation is caused by the addition of a separating agent, which takes the form of
another stream of matter or energy.
Usually the energy input required for the separation is supplied with the separating
agent, and generally the separating agent will cause the formation of a second phase of
matter.
For example, in the evaporation steps in the separating agent is the heat (energy)
supplied to the evaporators; this causes the formation of a second (vapor) phase, which
the water preferentially enters.

In the extraction process in the separating agent is the diethylene glycol solvent(matter);
this forms a second phase which the aromatics enter selectively.

Energy for that separation is supplied as heat (not shown) to the regenerator, which
renews the solvent capacity of the circulating glycol by boiling out the extracted
aromatics.
Categorizations of Separation Processes
In some cases a separation device receives a heterogeneous feed consisting of more than one phase
of matter and simply serves to separate the phases from each other.

For example, a filter or a centrifuge serves to separate solid and liquid phases from a feed which may
be in the form of a slurry.

A Cottrell precipitator accomplishes the removal of fine solids or a mist from a gas stream by means of
an imposed electric field.
We shall call such processes mechanical separation processes.
Often a mechanical separation process is employed to segregate the product phases in
one of these processes. We shall call these diffusional separation processes
Most diffusional separation processes operate through equilibration of two immiscible
phases which have different compositions at equilibrium.
Examples are the evaporation, crystallization, distillation, and extraction processes. We
shall call these equilibration processes.
On the other hand, some separation processes work by virtue of differences in transport
rate through some medium under the impetus of an imposed force, resulting from a
gradient in pressure, temperature, composition, electric potential, or the like.
Usually rate-governed processes give product phases that would be fully miscible if
mixed with each other, whereas ordinary equilibration processes necessarily generate
products that are immiscible with each other. Summarizing, we can categorize
separation processes in several ways:

Mechanical (heterogeneous-feed) vs. diffusional (homogeneous-feed) processes

Equilibration processes vs. rate-governed processes
Energy-separating-agent vs. mass-separating-agent processes
A relatively new subcategory of equilibration processes is that of imposed gradient
equilibration processes
As an example, the process of isoelectric focusing is used to separate amphoteric
molecules, e.g., proteins, according to their isoelectric pH values.
Above a certain pH an amphoteric molecule will carry a net negative charge; in a protein
this is attributable to ionized carboxylic acid groups.
Below this certain pH the amphoteric molecule will carry a net positive charge; in a
protein this is attributable to ionized amino groups which have formed while the
carboxylic acid groups become nondissociated.
The zero charge pH, or isoelectric point, varies from substance to substance.
In isoelectric focusing a gradient of pH is imposed over a distance in a complex fashion,
using substances called ampholytes
If an electric field is imposed in the same direction as the pH gradient, a gradient of
force on the molecules of a given substance will result, stemming from the change in
the charge per molecule as the Ph changes.
The force is directed toward the position of the isoelectric point for both higher and
lower pH values; at the isoelectric point the force is zero
Therefore the amphoteric molecule will migrate toward the position where the pH
equals its isoelectric pH and will stay there.
Substances with different isoelectric points migrate to different locations and thus
separate.
The imposed-gradient equilibration process creates a force gradient from positive to
negative values, through zero, by combining two imposed gradients. In isoelectric
focusing these are the gradient from the electric field and the pH gradient.

A corresponding rate-governed separation process results from removing the second

gradient, in this case the pH gradient.
The imposed electric field in a medium of constant pH would cause differently charged
species to migrate at different rates toward one electrode or the other, and different
species could be isolated at different points by introducing the feed as a pulse to one
location and waiting an appropriate length of time.

This process, known as electrophoresis, is fundamentally different from isoelectric

focusing since electrophoresis utilizes differences in rates of migration (charge-to-mass
ratio) whereas isoelectric focusing separates according to differences in isoelectric pH.
Imposed-gradient equilibration processes differ from ordinary equilibration processes in
that the products are miscible with each other and the separation will not occur without
the imposed field.
Some separation processes utilize more than one separating agent, e.g., both an energy
separating agent and a mass separating agent.
An example is extractive distillation:
a mixture of components with close boiling points is separated by adding a solvent
(mass separating agent), which serves to volatilize some components to greater
extents than others, and then using heat energy (energy separating agent) in a
distillation scheme of repeated vaporizations and condensations to generate a more
volatile product and a less volatile product.
Table 1-1 lists a large number of separation processes divided into the categories we
have just considered. The table shows the phases of matter involved, the separating
agent, and the physical or chemical principle on which the separation is based.

For mechanical processes the classification is by the principle involved. A practical

example is given in each case. References are given to more extensive descriptions of
each process. The table is not intended to be complete but to indicate the wide variety
of separation methods which have been practiced.
The capabilities of the methods indicated in Table 1-1 can be further expanded by
chemical derivitization, in which the components to be separated are subjected to some
form of chemical reaction.

Either some components react and others do not, or else all react, such that the
products are more readily separable than the initial unreacted mixture.
Some examples are the following
 Laser separation of isotopes:
Here the idea is to cause one of the isotopes to enter an activated state selectively,
using a laser of carefully determined and controlled emission frequency. If the result is
selective ionization, a subsequent ion-deflection device can be used to separate the
isotope mixture
Separation of optical isomers by selective reaction with enzymes
Plasma chromatography:
The components of a mixture are ionized to various extents and made to undergo
different times of flight in an electric field
In a number of cases several variations are possible on the methods listed in Table 1-1.
As an example, foam and bubble fractionation and flotation methods can be classified
according to the scheme shown
All the processes shown effect a separation through differences in surface activity of
different components
In foam fractionation, foam bubbles rise and liquid drains between the cells of a foam,
transporting the surface-active species selectively upward.
The species recovered in this way can be either surface-active themselves, e.g.,
detergents, or substances that react selectively with a surfactant, e.g., certain heavy
metals with anionic surfactants.
Alternatively, the process can be operating with a swarm of air bubbles rising through
an elongated liquid pool, the surface-active species being drawn off from the top of the
pool; this approach is known as BUBBLE FRACTIONATION.
In variants of bubble fractionation, a solvent is used to extract and collect the
surface-active species at the top of the pool (solvent sublation), or else the
surface-active species are collected in a layer of foam at the top of the pool
(combined bubble and foam fractionation).

Flotation processes, on the other hand, recover solid particles or scums from a
suspension in liquid and are therefore mechanical separation processes.
Ore flotation has been a major method of separation for years in the mineral
industry.

Macroflotation and microflotation refer to recovery of relatively large and small

particles, respectively.

In precipitate flotation a chemical agent is added to precipitate one or more

components selectively from solution as fine particles (chemical derivitization); these
particles are then removed by flotation.
In ion and molecular flotation a surfactant forms an insoluble compound with the
ion or molecule to be removed, and the substance undergoes flotation and is removed
as a scum.

Finally, in adsorbing colloid flotation a colloidal substance added to a solution adsorbs

the substance of interest and is removed by flotation.
Lee, et al. (1977) have proposed classifying separation processes by three
vectors, the size of the molecules or particles involved, the nature of the driving force
causing transport (concentration, electric, magnetic, etc.), and the flow and or design
configuration of the separator.

This approach appears particularly useful for categorising rate-governed separations

and indicating promising new methods.
Separations by centrifuging are indicative of the interaction between molecule or
particle size and the size of driving force required to achieve separation.

Conventional sedimentation centrifuges, with speeds in the range of 1000 to 50,000 r/

min, are widely used for separating particulate solids from liquids on the basis of density
difference.

Much higher speeds must be used in ultracentrifuges, which can separate biological cell
constituents, macromolecules, and even isotopes
The higher speeds are required to create forces large enough to move these much
smaller particles or molecules.

Alternatively, ultracentrifuges and centrifuges can be made to work on the isopycnic

principle as an imposed-gradient equilibration process by creating a density gradient
within the centrifuge and withdrawing products at the zones corresponding to their
individual densities.

The density gradient can be created by such methods as adding stratified layers of
sucrose solutions of different strengths or imposing a magnetic field upon a suspension
of magnetic material.
Yet another form of centrifugation uses the basket filter to make a separation based
upon size rather than density. Larger particles cannot pass through the openings
provided.
Separation Factor
The degree of separation which can be obtained with any particular separation process
is indicated by the separation factor.

Since the object of a separation device is to produce products of differing compositions,

it is logical to define the separation factor in terms of product compositions
The separation factor of j between components / and j is the ratio of the mole fractions
of those two components in product 1 divided by the ratio in product 2.
The separation factor will remain unchanged if all the mole fractions are replaced by
weight fractions, by molar flow rates of the individual components, or by mass flow rates
of the individual components.
INHERENT SEPARATION FACTORS: EQUILIBRATION
PROCESSES